CN102785420B - Heat-stabilised poly(ethylene naphthalate) film for flexible electronic and opto-electronic devices - Google Patents
Heat-stabilised poly(ethylene naphthalate) film for flexible electronic and opto-electronic devices Download PDFInfo
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Abstract
本发明提供用于柔性电子器件和光电子器件的热稳定聚萘二甲酸乙二醇酯膜。本发明涉及一种包括基材层和基材层表面上的阻隔层的复合膜,其中所述基材为包含聚萘二甲酸乙二醇酯的热稳定、热定形、取向膜,该取向膜在230℃、30分钟的收缩率低于0.5%,其中所述阻隔层包括无机层。The present invention provides thermally stable polyethylene naphthalate films for use in flexible electronic and optoelectronic devices. The invention relates to a composite film comprising a substrate layer and a barrier layer on the surface of the substrate layer, wherein the substrate is a thermally stable, heat-settable, oriented film comprising polyethylene naphthalate, the oriented film The shrinkage at 230°C for 30 minutes is less than 0.5%, wherein the barrier layer includes an inorganic layer.
Description
本申请是申请日为2002年9月10日、分案提交日为2008年8月5日、申请号为200810146087.8、发明名称为“用于柔性电子器件和光电子器件的热稳定聚萘二甲酸乙二醇酯膜”的分案申请的再次分案申请,其中,申请号为200810146087.8的分案申请是PCT申请号为PCT/GB02/04112(其进入国家阶段的申请号为02817576.X)、申请日为2002年9月10日、发明名称为“用于柔性电子器件和光电子器件的热稳定聚萘二甲酸乙二醇酯膜”的发明专利申请的分案申请。This application has an application date of September 10, 2002, a divisional submission date of August 5, 2008, an application number of 200810146087.8, and an invention title of "Heat-stabilized polyethylene naphthalate for flexible electronic devices and optoelectronic devices." The second divisional application of the divisional application of "diol ester film", among which, the divisional application with application number 200810146087.8 is PCT application number PCT/GB02/04112 (the application number of which entered the national phase is 02817576.X), application The date is September 10, 2002, and the invention title is a divisional application of the invention patent application titled "thermally stable polyethylene naphthalate film for flexible electronic devices and optoelectronic devices".
技术领域 technical field
本发明涉及在柔性电子器件和光电子器件,特别是场致发光(EL)显示器件,并尤其是有机发光显示(OLED)器件中适合作为基材的聚萘二甲酸乙二醇酯(PEN)膜。The present invention relates to polyethylene naphthalate (PEN) films suitable as substrates in flexible electronic and optoelectronic devices, especially electroluminescent (EL) display devices, and especially organic light emitting display (OLED) devices .
背景技术 Background technique
场致发光(EL)显示是以优异明视度(包括高的光亮度、高的对比度、非常快的响应速度和宽的视角)、极薄的外形和极低的能耗为特征的自发光显示模式。EL显示器件如阴极射线管(CRT)、荧光和等离子体显示器一样自身发光。其与液晶显示器(LCD)不同,无需背面照明。EL的响应速度可快至LCD的1000倍,使得这种方式特别适合于移动图像。EL显示器可用于众多用途,包括飞机和船舰控制器,汽车声频设备,计算器、移动电话、手提电脑、仪器仪表、工厂监视器和电子医疗设备。EL显示器的另一主要用途是作为光源,特别是作为小LCD表盘的背后照明以使它们在低的环境光照条件下易于读取。Electroluminescence (EL) display is a self-luminous display characterized by excellent brightness (including high brightness, high contrast, very fast response speed and wide viewing angle), extremely thin shape and extremely low energy consumption. display mode. EL display devices emit light by themselves like cathode ray tubes (CRT), fluorescent and plasma displays. Unlike liquid crystal displays (LCDs), they do not require backlighting. The response speed of EL can be as fast as 1000 times that of LCD, making this method especially suitable for moving images. EL displays are used in numerous applications, including aircraft and ship controllers, automotive audio equipment, calculators, mobile phones, laptop computers, instrumentation, factory monitors, and electronic medical equipment. Another major use of EL displays is as a light source, especially as a backlight for small LCD dials to make them easy to read in low ambient light conditions.
EL显示器通过在两块板中包夹一块磷光物质或其它场致发光物质的薄膜来起作用,各个板包括预定型样的导电组件,即电极,由此在显示器上形成可寻址的像素。所述电极是在场致发光物质上或者在单独载体上形成的涂层。当电极能透光时,例如使用透明导电金属氧化物时,电极为半透明或透明涂层的形式。同样,载体可根据需要半透明或透明。一般来说,至少阳极是透明的。载体通常起电极基板的作用或作为绝缘层。基材也提供使用、存贮和运输时防止化学和物理损伤的作用。目前有玻璃以及聚合物膜等用作绝缘载体。EL displays function by sandwiching a thin film of phosphorescent or other electroluminescent material between two plates, each plate including a predetermined pattern of conductive elements, ie electrodes, thereby forming addressable pixels on the display. The electrodes are coatings formed on the electroluminescent substance or on a separate carrier. When the electrodes are light-transmissive, such as when using transparent conductive metal oxides, the electrodes are in the form of translucent or transparent coatings. Likewise, the support can be translucent or transparent as desired. Generally, at least the anode is transparent. The carrier usually functions as an electrode substrate or as an insulating layer. The substrate also provides protection from chemical and physical damage during use, storage and transportation. Glass and polymer films are currently used as insulating carriers.
目前EL显示器件使用的阴极材料有许多。早期的研究人员使用碱金属。其它阴极材料包括金属复合物,诸如黄铜和导电金属氧化物(例如氧化铟锡)。人们也使用各种单一金属阴极,诸如铟、银、锡、铅、镁、锰和铝。There are many cathode materials used in EL display devices at present. Early researchers used alkali metals. Other cathode materials include metal composites such as brass and conductive metal oxides such as indium tin oxide. Various single metal cathodes have also been used, such as indium, silver, tin, lead, magnesium, manganese and aluminum.
在EL制作中最近的发现包括各种其有机发光介质由隔开阳极和阴极的两个极薄层(总厚度<1.0μm)组成的器件。OLED器件的代表性例子有公开于例如US4720432中的OLED。Recent discoveries in EL fabrication include various devices whose organic light-emitting medium consists of two very thin layers (total thickness <1.0 μm) separating the anode and cathode. Representative examples of OLED devices are OLEDs as disclosed in eg US4720432.
当电流通过导电组件时,场致发光材料发光。身为发光工艺而非如LCD显示器那样开关光源的EL显示器对于所有光照条件下均要求高明视度的应用来说特别有用。The electroluminescent material emits light when electrical current is passed through the conductive components. EL displays, which are light-emitting processes rather than switching light sources like LCD displays, are particularly useful for applications that require high visibility in all lighting conditions.
可产生极高纯度三原色的新的有机场致发光材料的开发使得可以制备具均匀水平光亮度和寿命的彩色显示器。可将具有这种特征的聚合物溶解于溶剂中并由溶液加工,使得可印刷电子器件。导电共轭聚合物特别有意义。此中所用的术语“共轭导电聚合物”是指沿其主链具有π-电子离域效应的聚合物。这种类型的聚合物可参见W.J.Feast在Polymer,37卷(22),5017-5047,1996中的综述。在一优选的实施方案中,共轭导电聚合物选自:The development of new organic electroluminescent materials that can produce the three primary colors with extremely high purity makes it possible to prepare color displays with uniform levels of luminance and lifetime. Polymers with such characteristics can be dissolved in solvents and processed from solution, making it possible to print electronic devices. Conductive conjugated polymers are of particular interest. The term "conjugated conductive polymer" as used herein refers to a polymer having π-electron delocalization along its main chain. Polymers of this type can be found in the review by W.J. Feast in Polymer, Vol. 37 (22), 5017-5047, 1996. In a preferred embodiment, the conjugated conductive polymer is selected from:
(i)烃共轭聚合物,诸如聚乙炔、聚亚苯基和聚(对-phenylenevinylene);(i) hydrocarbon conjugated polymers such as polyacetylene, polyphenylene and poly(p-phenylenevinylene);
(ii)在主链上具有杂原子的共轭杂环聚合物,诸如聚噻吩、聚吡咯和聚苯胺;和(ii) conjugated heterocyclic polymers having heteroatoms on the main chain, such as polythiophene, polypyrrole and polyaniline; and
(iii)含至少两个、优选至少三个、优选至少四个、优选至少五个、更优选六个或更多个重复亚单位的共轭低聚物,诸如低聚噻吩、低聚吡咯、低聚苯胺、低聚亚苯基和低聚(phenylene vinylene)。(iii) Conjugated oligomers containing at least two, preferably at least three, preferably at least four, preferably at least five, more preferably six or more repeating subunits, such as oligothiophene, oligopyrrole, Oligoaniline, oligophenylene and oligo(phenylene vinylene).
除了用于EL器件外,有人将这种共轭导电聚合物用于各种其它电子器件和光电子器件,包括光电池和半导体器件(诸如有机场效应晶体管、薄膜晶体管和通用集成电路)。In addition to their use in EL devices, such conjugated conductive polymers have been used in a variety of other electronic and optoelectronic devices, including photovoltaic cells and semiconductor devices such as organic field effect transistors, thin film transistors and general integrated circuits.
本发明涉及包含共轭导电聚合物的电子或光电子器件的绝缘和载体基材,包括EL器件(特别是OLED)、光电池和半导体器件(诸如有机场效应晶体管、薄膜晶体管和通用集成电路)的基材。本发明具体涉及光电子器件的基材,特别是EL器件(特别是OLED)或光电池的基材,尤其是EL器件(特别是OLED)的基材。The present invention relates to insulating and carrier substrates for electronic or optoelectronic devices comprising conjugated conducting polymers, including substrates for EL devices (especially OLEDs), photovoltaic cells and semiconductor devices such as organic field effect transistors, thin film transistors and general integrated circuits. material. The invention relates in particular to substrates for optoelectronic devices, especially EL devices, especially OLEDs, or photovoltaic cells, especially EL devices, especially OLEDs.
所述基材可以透明、半透明或不透明,但通常是透明的。所述基材通常需要满足光学透明度、平整度和最小双折率的严格技术要求。一般来说,对于显示器用途来说需要在400-800nm的区间均具有85%的总透光率(TLT)连同低于0.7%的雾度。要求表面光滑度和平整度能确保随后施加的涂层诸如电极导电涂层的完整性。所述基材也应具有良好的阻隔性,即对气体和溶剂渗透的高耐性。用于电子显示器用途的基材适合展现出低于10-6g/m2/天的水蒸气透过率和低于10-5/mL/m2/天的氧气透过率。机械性质诸如柔性、抗冲击性、硬度和耐画痕性也是重要的考虑因素。The substrate can be transparent, translucent or opaque, but is usually transparent. The substrates typically need to meet stringent specifications for optical clarity, flatness, and minimum birefringence. In general, a total light transmittance (TLT) of 85% in the region of 400-800 nm together with a haze of less than 0.7% is required for display applications. Surface smoothness and flatness are required to ensure the integrity of subsequently applied coatings such as electrode conductive coatings. The substrate should also have good barrier properties, ie high resistance to gas and solvent permeation. Substrates for electronic display applications suitably exhibit a water vapor transmission rate of less than 10 −6 g/m 2 /day and an oxygen transmission rate of less than 10 −5 /mL/m 2 /day. Mechanical properties such as flexibility, impact resistance, hardness and scratch resistance are also important considerations.
先前光学质量玻璃或石英一直在电子显示器应用中用作基材。这些材料能满足光学和平整性方面的要求并且具有良好的耐热性和耐化学性以及阻隔性。然而,这些材料并没有一些所需的机械性质,最明显的是低密度、柔性和抗冲击性。Optical quality glass or quartz has historically been used as a substrate in electronic display applications. These materials meet optical and planarity requirements and have good heat and chemical resistance as well as barrier properties. However, these materials do not have some desirable mechanical properties, most notably low density, flexibility and impact resistance.
为了改善机械性能,有人提出用塑料材料替代玻璃或石英片。塑料基材具有更大的柔性和改善的抗冲击性,并且比相同厚度的玻璃或石英片重量更轻。此外,柔性塑料基材可允许例如使用上述的共轭聚合物以卷对卷法将电子器件印刷在基材上,这可降低费用并可生产曲线表面的器件。但是,使用聚合材料的缺点是其较低的耐化学性和差的阻隔性。但是,人们开发了各种阻隔涂层来缓解这个问题。这些涂层通常用喷镀法在高温下施加,其中可控制涂层的密度和形态结构从而得到所需的阻隔性。阻隔层可以是有机阻隔层,也可以是无机阻隔层,其应展现出对沉积其上的沉积层良好的亲和性,并且能形成光滑表面。适合用于形成阻隔层的材料公开于例如US-6,198,217。为了确保阻隔层的完整性和防止其中的“针刺”,聚合物基材表面必须展现出良好的光滑性。In order to improve the mechanical properties, it has been proposed to replace glass or quartz plates with plastic materials. Plastic substrates offer greater flexibility and improved impact resistance, and are lighter in weight than glass or quartz sheets of the same thickness. In addition, flexible plastic substrates may allow electronic devices to be printed on the substrate in a roll-to-roll process, for example using the conjugated polymers described above, which reduces cost and allows the production of curved surface devices. However, the disadvantages of using polymeric materials are their lower chemical resistance and poor barrier properties. However, various barrier coatings have been developed to alleviate this problem. These coatings are usually applied by sputtering at high temperature, where the density and morphology of the coating can be controlled to obtain the desired barrier properties. The barrier layer, which may be an organic barrier layer or an inorganic barrier layer, should exhibit a good affinity for the deposited layer deposited thereon and be able to form a smooth surface. Materials suitable for use in forming barrier layers are disclosed, for example, in US-6,198,217. To ensure the integrity of the barrier layer and prevent "needling" within it, the surface of the polymeric substrate must exhibit good smoothness.
然而,用阻隔层涂层的塑料基材仍有许多限制。具体地说,沉积阻隔层中高温技术诸如喷镀的使用意味着聚合基材必须在高温下保持尺寸的稳定性。在生产显示器器件的加工条件下,特别是高温下,许多类型的聚合物基材会出现不可接受的尺寸变形诸如卷曲。这些因素意味着只有某些类型的聚合物膜适合作为这种器件的基材。此外,为了降低尺寸的不稳定性,仍然需要限制生产过程的温度诸如阻隔层沉积过程的温度。因为涂层的质量通常随沉积过程温度提高,也需要提供可在较高温度下加工并同时保持尺寸稳定性的基材。此外,因为对于聚合物基材来说通常需要另外的阻隔层,由此以阻隔涂层的膨胀校正聚合物基材的膨胀,由此避免卷曲和保持平整。因为这些原因,基材的膨胀特性需要较小或可预测并优选同时具有两者。However, plastic substrates coated with barrier layers still have many limitations. In particular, the use of high temperature techniques such as sputtering in depositing barrier layers means that the polymeric substrate must remain dimensional stable at high temperatures. Under the processing conditions used to produce display devices, especially high temperatures, many types of polymeric substrates can exhibit unacceptable dimensional distortions such as curling. These factors mean that only certain types of polymer films are suitable as substrates for such devices. Furthermore, in order to reduce the dimensional instability, it is still necessary to limit the temperature of the production process such as the temperature of the barrier layer deposition process. Because the quality of coatings generally increases with deposition process temperature, there is also a need to provide substrates that can be processed at higher temperatures while maintaining dimensional stability. Furthermore, since an additional barrier layer is generally required for polymeric substrates, the expansion of the polymeric substrate is thereby corrected for with the expansion of the barrier coating, thereby avoiding curling and keeping it flat. For these reasons, the expansion characteristics of the substrate need to be small or predictable and preferably both.
配置电子显示器件的设备,特别是手持设备诸如移动电话的生产商通常使用称为“热循环”的测试来评价显示器件的性能。该测试包括将显示器循环暴露于约-40℃到约80℃的温度下,每个温度有预定的“保持时间”,温度间有一定的过渡时间,并且会模拟最极端的操作条件。Manufacturers of equipment incorporating electronic display devices, particularly handheld devices such as mobile phones, commonly use a test known as "thermal cycling" to evaluate the performance of display devices. The test involves cyclically exposing the display to temperatures ranging from about -40°C to about 80°C, with predetermined "hold times" at each temperature, with transition times between temperatures, and simulates the most extreme operating conditions.
一直以来均难以生产具有所需尺寸稳定性的聚合物基材。It has been difficult to produce polymeric substrates with the required dimensional stability.
迄今,适用于电子显示器用途的聚合物基材通常是无定形的浇铸聚合物膜,包括具有较高玻璃化转变温度(Tg)的聚合物如聚醚砜和聚酰亚胺。具有高Tg的聚合物一直受欢迎,因为聚合物的性质在Tg以上会变化,特别是在Tg以上尺寸稳定性较难以预测和控制。除了伴随着生产要求尺寸稳定性和平整性的膜的问题外,已知的膜也可具有吸收湿气的倾向,导致可变和不可预测的膨胀特性。此外,使用溶剂浇铸技术生产的膜可能包含残留溶剂并需要脱气。To date, polymer substrates suitable for electronic display applications have generally been amorphous cast polymer films, including polymers with relatively high glass transition temperatures (Tg) such as polyethersulfone and polyimide. Polymers with high Tg have always been favored because the properties of polymers change above Tg, especially dimensional stability above Tg is difficult to predict and control. In addition to the problems associated with producing films that require dimensional stability and flatness, known films can also have a tendency to absorb moisture, resulting in variable and unpredictable swelling characteristics. Additionally, membranes produced using solvent casting techniques may contain residual solvents and require degassing.
发明内容 Contents of the invention
本发明的一个目的是提供一种克服了至少一种前述问题的膜。具体地说,本发明的一个目的是提供一种在生产包含共轭导电聚合物的电子器件或光电子器件中适合用作基材,特别是柔性基材的具良好高温尺寸稳定性的聚合物膜,包括用于EL器件(特别是OLED),光电池和半导体器件(诸如有机场效应晶体管、薄膜晶体管和通用集成电路)的基材。本发明的另一目的是提供具良好高温尺寸稳定性、高光学透明性和良好表面光滑性/平整性的聚合物膜。It is an object of the present invention to provide a membrane which overcomes at least one of the aforementioned problems. In particular, it is an object of the present invention to provide a polymer film having good high-temperature dimensional stability suitable for use as a substrate, in particular a flexible substrate, in the production of electronic or optoelectronic devices comprising conjugated conducting polymers , including substrates for EL devices (especially OLEDs), photovoltaic cells, and semiconductor devices (such as organic field-effect transistors, thin-film transistors, and general-purpose integrated circuits). Another object of the present invention is to provide polymer films with good high temperature dimensional stability, high optical clarity and good surface smoothness/planarity.
按照本发明,提供了包含聚萘二甲酸乙二醇酯的热稳定、热定形取向膜在含共轭导电聚合物的电子或光电子器件中或在这些器件的制造中作为基材的用途,其中所述膜在230℃、30分钟具有低于1%的收缩率,并优选其中所述膜在从8℃加热到200℃并然后冷却到8℃这一过程前后在25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%。According to the present invention there is provided the use of a thermally stable, heat-set oriented film comprising polyethylene naphthalate as a substrate in electronic or optoelectronic devices comprising conjugated conducting polymers or in the manufacture of these devices, wherein The film has a shrinkage of less than 1% at 230°C for 30 minutes and preferably wherein the film has a residual dimension measured at 25°C before and after heating from 8°C to 200°C and then cooling to 8°C The change ΔL r is less than 0.75% of the original size.
本发明还提供:The present invention also provides:
(1).一种制备复合膜的方法,该复合膜包括基材层和基材层表面上的阻隔层,其中所述基材为包含聚萘二甲酸乙二醇酯的热稳定、热定形、取向膜,该取向膜在230℃、30分钟的收缩率低于1%,所述方法包括下面步骤:(1). A method for preparing a composite film, the composite film comprising a substrate layer and a barrier layer on the surface of the substrate layer, wherein the substrate is a thermally stable, heat-settable film comprising polyethylene naphthalate , an alignment film, the shrinkage rate of the alignment film at 230° C. for 30 minutes is lower than 1%, and the method comprises the following steps:
(i)形成包含聚萘二甲酸乙二醇酯的层;(i) forming a layer comprising polyethylene naphthalate;
(ii)在至少一个方向拉伸所述层;(ii) stretching the layer in at least one direction;
(iii)在尺寸限定下以19-75kg/m膜宽的张力在高于聚酯的玻璃化转变温度但低于其熔融温度的温度下热定形;和(iii) heat-set at a temperature above the glass transition temperature of the polyester but below its melting temperature at a tension of 19-75 kg/m film width under dimensional constraints; and
(iv)在低于5kg/m膜宽的张力和在高于聚酯的玻璃化转变温度但低于其熔融温度的温度下热稳定,(iv) thermally stable at tensions below 5 kg/m film width and at temperatures above the glass transition temperature of the polyester but below its melting temperature,
(v)在所述基材的表面沉积阻隔层。(v) depositing a barrier layer on the surface of said substrate.
(2).(1)的方法,其中所述热稳定步骤离线进行。(2). The method of (1), wherein the thermal stabilization step is performed offline.
(3).(1)或(2)的方法,其中所述热稳定在1.0-2.5kg/m膜宽度的张力范围内进行。(3). The method of (1) or (2), wherein the thermal stabilization is performed within a tension range of 1.0 to 2.5 kg/m film width.
(4).(1)或(2)的方法,其中所述热定形在45-50kg/m膜宽度的张力范围内进行。(4). The method of (1) or (2), wherein the heat setting is performed within a tension range of 45-50 kg/m film width.
(5).(1)或(2)的方法,其中所述热稳定在190-250℃的温度范围内实现。(5). The method of (1) or (2), wherein the thermal stabilization is achieved within a temperature range of 190-250°C.
(6).(1)或(2)的方法,其中所述热稳定在200-230℃的温度范围内实现。(6). The method of (1) or (2), wherein the thermal stabilization is achieved within a temperature range of 200-230°C.
(7).(1)或(2)的方法,其中所述热定形在235-240℃的温度范围内实现。(7). The method of (1) or (2), wherein the heat setting is carried out within a temperature range of 235-240°C.
(8).(1)或(2)的方法,进一步包括:(8). The method of (1) or (2), further comprising:
(vi)在所述阻隔层的至少一部分上施加导电材料。(vi) applying a conductive material to at least a portion of said barrier layer.
(9).(8)的方法,其中所述导电材料包括导电金属氧化物。(9). The method of (8), wherein the conductive material includes a conductive metal oxide.
(10).(8)的方法,其中所述导电材料包括氧化铟锡。(10). The method of (8), wherein the conductive material includes indium tin oxide.
(11).(8)的方法,进一步包括:(11). The method of (8), further comprising:
(vii)提供导电共轭聚合物层。(vii) providing a conductive conjugated polymer layer.
(12).(1)或(2)的方法,其中所述聚萘二甲酸乙二醇酯衍生自2,6-萘二甲酸。(12). The method of (1) or (2), wherein the polyethylene naphthalate is derived from 2,6-naphthalene dicarboxylic acid.
(13).(1)或(2)的方法,其中所述聚萘二甲酸乙二醇酯的特性粘度为0.5-1.5。(13). The method of (1) or (2), wherein the polyethylene naphthalate has an intrinsic viscosity of 0.5 to 1.5.
(14).(1)或(2)的方法,其中所述热稳定、热定形、取向膜的散射可见光百分比小于1.5%。(14). The method of (1) or (2), wherein the heat-stable, heat-set, oriented film has a percentage of scattered visible light of less than 1.5%.
(15).(1)或(2)的方法,其中所述热稳定、热定形、取向膜为双轴取向。(15). The method of (1) or (2), wherein the thermally stable, heat-set, oriented film is biaxially oriented.
(16).(1)或(2)的方法,其中所述基材在230℃、30分钟的收缩率低于0.5%。(16). The method of (1) or (2), wherein the substrate has a shrinkage rate of less than 0.5% at 230° C. for 30 minutes.
(17).(1)或(2)的方法,其中所述基材在从8℃加热到200℃,然后冷却到8℃这一过程前后于25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%。(17). The method of (1) or (2), wherein the remaining dimensional change ΔL r measured at 25°C before and after the substrate is heated from 8°C to 200°C and then cooled to 8°C is low 0.75% of original size.
(18).(1)或(2)的方法,其中所述基材在-40℃到+100℃的温度范围内具有低于40×10-6/℃的线性热膨胀系数CLTE。(18). The method of (1) or (2), wherein the substrate has a coefficient of linear thermal expansion CLTE of less than 40×10 −6 /° C. within a temperature range of -40° C. to +100° C.
(19).(1)或(2)的方法,其中所述阻隔层包括无机层。(19). The method of (1) or (2), wherein the barrier layer comprises an inorganic layer.
(20).(19)的方法,其中所述无机层包括选自SiO2、SiO、GeO、Al2O3、TiN和Si3N4的材料。(20). The method of (19), wherein the inorganic layer includes a material selected from SiO 2 , SiO, GeO, Al 2 O 3 , TiN, and Si 3 N 4 .
(21).一种包括基材层和基材层表面上的阻隔层的复合膜,其中所述基材为包含聚萘二甲酸乙二醇酯的热稳定、热定形、取向膜,该取向膜在230℃、30分钟的收缩率低于1%,所述复合膜还包括在阻隔层表面的至少一部分上的电极层。(21). A composite film comprising a substrate layer and a barrier layer on the surface of the substrate layer, wherein the substrate is a thermally stable, heat-settable, oriented film comprising polyethylene naphthalate, the orientation The shrinkage of the film is less than 1% at 230°C for 30 minutes, the composite film further comprising an electrode layer on at least a portion of the surface of the barrier layer.
(22).(21)的复合膜,其中所述电极层包括导电金属氧化物。(22). The composite film of (21), wherein the electrode layer comprises a conductive metal oxide.
(23).(21)的复合膜,其中所述电极层包括氧化铟锡。(23). The composite film of (21), wherein the electrode layer comprises indium tin oxide.
(24).(21)-(23)中任一项的复合膜,进一步包括共轭导电聚合物层。(24). The composite film of any one of (21)-(23), further comprising a conjugated conductive polymer layer.
(25).(21)-(23)中任一项的复合膜,其中所述聚萘二甲酸乙二醇酯衍生自2,6-萘二甲酸。(25). The composite film of any one of (21)-(23), wherein the polyethylene naphthalate is derived from 2,6-naphthalene dicarboxylic acid.
(26).(21)-(23)中任一项的复合膜,其中所述聚萘二甲酸乙二醇酯的特性粘度为0.5-1.5。(26). The composite film according to any one of (21) to (23), wherein the polyethylene naphthalate has an intrinsic viscosity of 0.5 to 1.5.
(27).(21)-(23)中任一项的复合膜,其中所述热稳定、热定形、取向膜的散射可见光百分比小于1.5%。(27). The composite film of any one of (21)-(23), wherein the thermally stable, heat-set, oriented film has a percent scattered visible light of less than 1.5%.
(28).(21)-(23)中任一项的复合膜,其中所述热稳定、热定形、取向膜为双轴取向。(28). The composite film of any one of (21)-(23), wherein the heat-stable, heat-set, oriented film is biaxially oriented.
(29).(21)-(23)中任一项的复合膜,其中所述基材在230℃、30分钟的收缩率低于0.5%。(29). The composite film according to any one of (21) to (23), wherein the substrate has a shrinkage rate of less than 0.5% at 230° C. for 30 minutes.
(30).(21)-(23)中任一项的复合膜,其中所述基材在从8℃加热到200℃,然后冷却到8℃这一过程前后于25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%。(30). The composite film according to any one of (21)-(23), wherein the remaining size of the substrate measured at 25°C before and after heating from 8°C to 200°C and then cooling to 8°C The change ΔL r is less than 0.75% of the original size.
(31).(21)-(23)中任一项的复合膜,其中所述基材在-40℃到+100℃的温度范围内具有低于40×10-6/℃的线性热膨胀系数CLTE。(31). The composite film according to any one of (21) to (23), wherein the substrate has a linear thermal expansion coefficient of less than 40×10 −6 /° C. in the temperature range from -40° C. to +100° C. CLTE.
(32).(21)-(23)中任一项的复合膜,其中所述阻隔层包括无机层。(32). The composite film of any one of (21)-(23), wherein the barrier layer comprises an inorganic layer.
(33).(32)的复合膜,其中所述无机层包括选自SiO2、SiO、GeO、Al2O3、TiN和Si3N4的材料。(33). The composite film of (32), wherein the inorganic layer includes a material selected from SiO 2 , SiO, GeO, Al 2 O 3 , TiN, and Si 3 N 4 .
(34).一种包含共轭导电聚合物的电子器件或光电子器件,其中所述器件包括(21)-(33)中任一项定义的复合膜。(34). An electronic or optoelectronic device comprising a conjugated conductive polymer, wherein the device comprises the composite film defined in any one of (21) to (33).
(35).(34)的器件,其为场致发光显示器件。(35). The device of (34), which is an electroluminescence display device.
(36).(34)的器件,其中所述器件为有机发光显示器件。(36). The device of (34), wherein the device is an organic light emitting display device.
(37).(34)的器件,其中所述器件为光电池或半导体器件。(37). The device of (34), wherein the device is a photovoltaic cell or a semiconductor device.
(38).(37)的器件,其中所述半导体器件选自有机场效应晶体管、薄膜晶体管和集成电路。(38). The device of (37), wherein the semiconductor device is selected from the group consisting of organic field effect transistors, thin film transistors and integrated circuits.
(39).包含聚萘二甲酸乙二醇酯的热稳定、热定形的取向膜在含共轭导电聚合物的电子器件或光电子器件中或在这些器件的制造中作为基材的用途,其中所述膜在230℃、30分钟具有低于0.5%的收缩率。(39). Use of a thermally stable, heat-settable alignment film comprising polyethylene naphthalate as a substrate in electronic or optoelectronic devices containing conjugated conductive polymers or in the manufacture of these devices, wherein The film has a shrinkage of less than 0.5% at 230°C for 30 minutes.
(40).(39)的用途,其中所述器件为光电子器件。(40). The use of (39), wherein the device is an optoelectronic device.
(41).(39)的用途,其中所述器件为场致发光显示器件。(41). The use of (39), wherein the device is an electroluminescence display device.
(42).(39)的用途,其中所述器件为有机发光显示器件。(42). The use of (39), wherein the device is an organic light emitting display device.
(43).(39)的用途,其中所述器件为光电池或半导体器件。(43). The use of (39), wherein the device is a photovoltaic cell or a semiconductor device.
(44).(39)的用途,其中所述基材在从8℃加热到200℃,然后冷却到8℃这一过程前后于25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%。(44). The use of (39), wherein the remaining dimensional change ΔL r measured at 25°C before and after the substrate is heated from 8°C to 200°C and then cooled to 8°C is lower than that of the original size 0.75%.
(45).(39)的用途,其中所述基材在-40℃到+100℃的温度范围内具有低于40×10-6/℃的线性热膨胀系数CLTE。(45). The use of (39), wherein the substrate has a coefficient of linear thermal expansion CLTE of less than 40×10 −6 /° C. in the temperature range from -40° C. to +100° C.
(46).(39)的用途,其中所述聚萘二甲酸乙二醇酯衍生自2,6-萘二甲酸。(46). The use of (39), wherein the polyethylene naphthalate is derived from 2,6-naphthalene dicarboxylic acid.
(47).(39)的用途,其中所述聚萘二甲酸乙二醇酯的特性粘度为0.5-1.5。(47). The use of (39), wherein the polyethylene naphthalate has an intrinsic viscosity of 0.5 to 1.5.
(48).(39)的用途,其中所述热稳定、热定形、取向膜的散射可见光百分比小于1.5%。(48). The use of (39), wherein the thermally stable, heat set, oriented film has a percent scattered visible light of less than 1.5%.
(49).(39)的用途,其中所述热稳定、热定形、取向膜为双轴取向。(49). The use of (39), wherein the heat stable, heat set, oriented film is biaxially oriented.
(50).一种制备电子器件或光电子器件的方法,该电子器件或光电子器件包含共轭导电聚合物和含热稳定、热定形的取向聚萘二甲酸乙二醇酯膜的基材,所述膜在230℃、30分钟的收缩率低于0.5%,所述方法包括下面步骤:(50). A method of preparing an electronic device or an optoelectronic device comprising a conjugated conductive polymer and a substrate comprising a thermally stable, heat-set oriented polyethylene naphthalate film, wherein The shrinkage of the film at 230° C. for 30 minutes is lower than 0.5%, and the method comprises the following steps:
(i)形成包含聚萘二甲酸乙二醇酯的层;(i) forming a layer comprising polyethylene naphthalate;
(ii)在至少一个方向拉伸所述层;(ii) stretching the layer in at least one direction;
(iii)在尺寸限定下以19-75kg/m膜宽的张力在高于聚酯的玻璃化转变温度但低于其熔融温度的温度下热定形;(iii) heat setting at a temperature above the glass transition temperature of the polyester but below its melting temperature at a tension of 19-75 kg/m film width under size constraints;
(iv)在低于5kg/m膜宽的张力和在高于聚酯的玻璃化转变温度但低于其熔融温度的温度下热稳定,其中所述热稳定温度在190-250℃的范围内;(iv) thermally stable at a tension lower than 5 kg/m film width and at a temperature higher than the glass transition temperature of the polyester but lower than its melting temperature, wherein the thermally stable temperature is in the range of 190-250°C ;
(v)将所得热稳定、热定形、取向膜作为基材提供在器件中。(v) Providing the resulting thermally stable, heat set, oriented film as a substrate in a device.
(51).(50)的方法,其中所述器件为光电子器件。(51). The method of (50), wherein the device is an optoelectronic device.
(52).(50)的方法,其中所述器件为场致发光显示器件。(52). The method of (50), wherein the device is an electroluminescence display device.
(53).(50)的方法,其中所述器件为有机发光显示器件。(53). The method of (50), wherein the device is an organic light emitting display device.
(54).(50)的方法,其中所述器件为光电池或半导体器件。(54). The method of (50), wherein the device is a photovoltaic cell or a semiconductor device.
(55).(50)的方法,其中所述基材在从8℃加热到200℃,然后冷却到8℃这一过程前后于25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%。(55). The method of (50), wherein the remaining dimensional change ΔL r measured at 25°C before and after the substrate is heated from 8°C to 200°C and then cooled to 8°C is lower than the original size 0.75%.
(56).(50)的方法,其中所述基材在-40℃到+100℃的温度范围内具有低于40×10-6/℃的线性热膨胀系数CLTE。(56). The method of (50), wherein the substrate has a coefficient of linear thermal expansion CLTE of less than 40×10 −6 /° C. within a temperature range of -40° C. to +100° C.
(57).(50)的方法,该方法还包括用阻隔层涂布所述热稳定、热定形、取向膜基材的步骤。(57). The method of (50), further comprising the step of coating said heat stable, heat set, oriented film substrate with a barrier layer.
(58).(57)的方法,该方法还包括通过将导电材料施加到至少一部分阻隔层上来提供电极的步骤。(58). The method of (57), further comprising the step of providing an electrode by applying a conductive material to at least a part of the barrier layer.
(59).(58)的方法,该方法还包括使导电共轭聚合物与所述电极接触的步骤。(59). The method of (58), further comprising the step of bringing a conductive conjugated polymer into contact with the electrode.
(60).(50)的方法,其中所述热稳定步骤离线进行。(60). The method of (50), wherein the thermal stabilization step is performed offline.
(61).(50)或(60)的方法,其中所述热稳定在1.0-2.5kg/m膜宽的张力范围内实现。(61). The method of (50) or (60), wherein the thermal stabilization is achieved within a tension range of 1.0-2.5 kg/m film width.
(62).(50)或(60)的方法,其中所述热定形在45-50kg/m膜宽的张力范围内实现。(62). The method of (50) or (60), wherein the heat setting is achieved within a tension range of 45-50 kg/m film width.
(63).(50)或(60)的方法,其中所述热稳定在200-230℃的温度范围内实现。(63). The method of (50) or (60), wherein the thermal stabilization is achieved within a temperature range of 200-230°C.
(64).(50)或(60)的方法,其中所述热定形在235-240℃的温度范围内实现。(64). The method of (50) or (60), wherein the heat setting is achieved at a temperature in the range of 235-240°C.
(65).(50)的方法,其中所述聚萘二甲酸乙二醇酯衍生自2,6-萘二甲酸。(65). The method of (50), wherein the polyethylene naphthalate is derived from 2,6-naphthalene dicarboxylic acid.
(66).(50)的方法,其中所述聚萘二甲酸乙二醇酯的特性粘度为0.5-1.5。(66). The method of (50), wherein the polyethylene naphthalate has an intrinsic viscosity of 0.5 to 1.5.
(67).(50)的方法,其中所述热稳定、热定形、取向膜的散射可见光百分比小于1.5%。(67). The method of (50), wherein the thermally stable, heat set, oriented film has a percent scattered visible light of less than 1.5%.
(68).(50)的方法,其中所述热稳定、热定形、取向膜为双轴取向。(68). The method of (50), wherein the thermally stable, heat set, oriented film is biaxially oriented.
(69).一种包括基材层和基材层表面上的阻隔层的复合膜,其中所述基材为包含聚萘二甲酸乙二醇酯的热稳定、热定形、取向膜,该取向膜在230℃、30分钟的收缩率低于0.5%。(69). A composite film comprising a substrate layer and a barrier layer on the surface of the substrate layer, wherein the substrate is a thermally stable, heat-settable, oriented film comprising polyethylene naphthalate, the orientation The shrinkage of the film at 230°C for 30 minutes is less than 0.5%.
(70).(69)的复合膜,其中所述基材在从8℃加热到200℃,然后冷却到8℃这一过程前后于25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%。(70). The composite film of (69), wherein the substrate is heated from 8°C to 200°C and then cooled to 8°C before and after the remaining dimensional change ΔL r measured at 25°C is lower than the original size 0.75%.
(71).(69)的复合膜,其中所述基材在-40℃到+100℃的温度范围内具有低于40×10-6/℃的线性热膨胀系数CLTE。(71). The composite film of (69), wherein the base material has a coefficient of linear thermal expansion CLTE of less than 40×10 −6 /° C. in the temperature range from -40° C. to +100° C.
(72).(69)的复合膜,其中所述聚萘二甲酸乙二醇酯衍生自2,6-萘二甲酸。(72). The composite film of (69), wherein the polyethylene naphthalate is derived from 2,6-naphthalene dicarboxylic acid.
(73).(69)的复合膜,其中所述聚萘二甲酸乙二醇酯的特性粘度为0.5-1.5。(73). The composite film of (69), wherein the polyethylene naphthalate has an intrinsic viscosity of 0.5 to 1.5.
(74).(69)的复合膜,其中所述热稳定、热定形、取向膜的散射可见光百分比小于1.5%。(74). The composite film of (69), wherein the thermally stable, heat set, oriented film has a percent scattered visible light of less than 1.5%.
(75).(69)的复合膜,其中所述热稳定、热定形、取向膜为双轴取向。(75). The composite film of (69), wherein the heat stable, heat set, oriented film is biaxially oriented.
此中所用的术语“含共轭导电聚合物的器件”优选是指EL器件(特别是OLED)、光电池和半导体器件(诸如有机场效应晶体管、薄膜晶体管和通用集成电路)。此中所用的术语“含共轭导电聚合物的光电子器件”优选是指EL器件(特别是OLED)和光电器件,并特别优选是指EL器件(特别是OLED)。此中所用的术语含共轭导电聚合物的电子器件不包括光电子器件,优选是指半导体器件诸如有机场效应晶体管、薄膜晶体管和通用集成电路,并特别是有机场效应晶体管。The term "conjugated conductive polymer-containing device" as used herein preferably refers to EL devices (especially OLEDs), photovoltaic cells, and semiconductor devices (such as organic field effect transistors, thin film transistors, and general integrated circuits). The term "optoelectronic device comprising a conjugated conductive polymer" as used herein preferably refers to EL devices (in particular OLEDs) and optoelectronic devices, and particularly preferably refers to EL devices (in particular OLEDs). The term conjugated conductive polymer-containing electronic device as used herein excludes optoelectronic devices and preferably refers to semiconductor devices such as organic field effect transistors, thin film transistors and general integrated circuits, and especially organic field effect transistors.
由于相对于所述器件制造中常用的温度和相对于在这种应用中先前所用聚合物的Tg来说,PENTg(约120℃)较低,PEN适合作为这种应用的基材是令人惊异的。热稳定、取向PEN膜的一项特殊好处是其允许在阻隔层沉积时使用较高的温度。此外,可以获得具有高透明性和良好表面光滑性的PEN膜表面。相对于聚对苯二甲酸亚乙酯(PET)膜来说,PEN膜的另一优点例如是其较低的水蒸气透过率和其较低的氧气透过率。就其低得多的湿气吸收率来说,已经发现PEN膜优于上面讨论的无定形高Tg聚合物膜。Due to the low g of PENT (about 120 °C) relative to the temperatures commonly used in the fabrication of such devices and relative to the T g of polymers previously used in this application, the suitability of PEN as a substrate for this application makes amazing. A particular benefit of thermally stable, oriented PEN films is that they allow the use of higher temperatures for barrier layer deposition. In addition, a PEN film surface with high transparency and good surface smoothness can be obtained. Another advantage of PEN films is, for example, its lower water vapor transmission rate and its lower oxygen transmission rate relative to polyethylene terephthalate (PET) films. In terms of its much lower moisture absorption rate, PEN films have been found to be superior to the amorphous high Tg polymer films discussed above.
在230℃、30分钟后所述膜优选具有低于0.75%、更优选低于0.5%、再更优选低于0.25%的收缩率。在一个实施方案中,所述膜在230℃、30分钟后的收缩率低于0.1%。所述膜在从8℃加热到200℃并然后冷却到8℃这一过程前后于25℃测得的剩余尺寸变化△Lr优选低于原尺寸的0.5%,更优选低于0.25%,再更优选低于0.1%。优选所述膜在-40℃到+100℃的温度范围内具有低于40×10-6/℃、优选低于30×10-6/℃、更优选低于25×10-6/℃、再更优选低于20×10-6/℃的线性热膨胀系数(CLTE)。The film preferably has a shrinkage of less than 0.75%, more preferably less than 0.5%, even more preferably less than 0.25% after 30 minutes at 230°C. In one embodiment, the film has a shrinkage of less than 0.1% after 30 minutes at 230°C. The remaining dimensional change ΔL r of the film measured at 25°C before and after heating from 8°C to 200°C and then cooling to 8°C is preferably less than 0.5% of the original size, more preferably less than 0.25%, and then More preferably less than 0.1%. Preferably the film has a temperature range of -40°C to +100°C of less than 40×10 -6 /°C, preferably less than 30×10 -6 /°C, more preferably less than 25×10 -6 /°C, Still more preferred is a coefficient of linear thermal expansion (CLTE) of less than 20 x 10 -6 /°C.
所述膜是自载膜,就是说它能在没有载基的情况下独立存在。The membrane is a self-supporting membrane, that is to say it can exist independently without a support.
所述膜的厚度优选为约12-300μm,更优选约25-250μm,再更优选约50-250μm。The thickness of the film is preferably about 12-300 μm, more preferably about 25-250 μm, still more preferably about 50-250 μm.
PEN聚酯可通过常规方法合成。一种典型的方法涉及直接酯化或酯交换反应,并接着进行缩聚。因此,PEN聚酯可通过将2,5-、2,6-或2,7-萘二甲酸(优选2,6-萘二甲酸)或其低级烷基(至多6个碳原子)二酯与乙二醇的缩合来获得。一般来说,缩聚反应包括固相聚合阶段。所述固相聚合可在流化床如氮气流化的流化床或在使用旋转真空干燥器的真空流化床上进行。适合的固相聚合技术公开于例如EP-A-0419400中,该专利内容通过引用并入本文。PEN polyester can be synthesized by conventional methods. A typical method involves direct esterification or transesterification followed by polycondensation. Thus, PEN polyesters can be obtained by combining 2,5-, 2,6- or 2,7-naphthalene dicarboxylic acid (preferably 2,6-naphthalene dicarboxylic acid) or its lower alkyl (up to 6 carbon atoms) diester with obtained by condensation of ethylene glycol. In general, polycondensation reactions include a solid phase polymerization stage. The solid phase polymerization may be carried out in a fluidized bed such as a nitrogen fluidized fluidized bed or in a vacuum fluidized bed using a rotary vacuum drier. Suitable solid state polymerization techniques are disclosed in, for example, EP-A-0419400, the contents of which are incorporated herein by reference.
在一优选的实施方案中,所述PEN使用锗催化剂制备,其提供了降低了污染物如催化剂残留物、不需要的无机沉积物和其它聚合副产物的水平的聚合物材料。作为“更清洁”聚合组合物的结果,由其制造的膜展现出得到改善的光学透明性和表面光滑性。In a preferred embodiment, the PEN is prepared using a germanium catalyst, which provides a polymeric material with reduced levels of contaminants such as catalyst residues, unwanted inorganic deposits, and other polymerization by-products. As a result of the "cleaner" polymeric composition, films made therefrom exhibit improved optical clarity and surface smoothness.
用于制备本发明的膜的PEN适合具有0.5-1.5、优选0.7-1.5、特别是0.79-1.0的PET-等效特性粘度(IV;如本文所述测定)。低于0.5的IV导致聚合物膜缺乏所需的性质诸如机械性质,而大于1.5的IV难以获得并且将可能导致原材料加工的困难。The PEN used to make the films of the invention suitably has a PET-equivalent intrinsic viscosity (IV; determined as described herein) of 0.5-1.5, preferably 0.7-1.5, especially 0.79-1.0. An IV below 0.5 results in a polymer film lacking desirable properties such as mechanical properties, while an IV above 1.5 is difficult to obtain and will likely lead to difficulties in raw material processing.
基材的形成可通过本领域技术人员熟悉的常规技术来进行。基材的形成适合按照下面所述的步骤通过挤压来进行。一般来说,所述方法包括挤出熔融聚合物层、骤冷挤出物并在至少一个方向对骤冷的挤出物进行取向的步骤。Formation of the substrate can be performed by conventional techniques familiar to those skilled in the art. Formation of the substrate is suitably carried out by extrusion according to the procedure described below. Generally, the method includes the steps of extruding a layer of molten polymer, quenching the extrudate, and orienting the quenched extrudate in at least one direction.
所述基材可以单轴取向,但是优选双轴取向。取向可通过本领域技术人员熟悉的任何制备取向膜的方法如管状法(tubular process)或平膜法(flat film process)来进行。双轴取向通过在膜的平面上以两个互相垂直的方向拉伸来进行,以获得令人满意的机械性质和物理性质的结合。The substrate may be uniaxially oriented, but is preferably biaxially oriented. Orientation can be performed by any method for preparing an oriented film familiar to those skilled in the art, such as tubular process or flat film process. Biaxial orientation is performed by stretching in two mutually perpendicular directions in the plane of the film to obtain a satisfactory combination of mechanical and physical properties.
在管状法中,同时双轴取向可通过通过挤出热塑性聚酯管并随后骤冷、重加热、再然后通过内部气压扩展来引起横向取向,并且以导致纵向取向的速率拉伸。In the tubular process, simultaneous biaxial orientation can be induced by extruding a thermoplastic polyester tube followed by quenching, reheating, and then expanding by internal air pressure, and stretching at a rate that results in machine direction orientation.
在优选的平膜法中,形成基材的聚酯通过缝型模头挤出并在冷却的铸造鼓上快速冷却以确保聚酯骤冷成无定形态。然后通过在高于所述聚酯玻璃化转变温度的温度下,在至少一个方向拉伸该骤冷的挤出物来进行取向。随后的取向可通过膜拉伸机首先在一个方向(通常纵向,即直向)拉伸平的经骤冷的挤出物,然后在横向拉伸来进行。挤出物的直向拉伸适合经一组转动辊或在两对压料辊间进行,然后横向拉伸在展幅机上进行。或者,取向可在挤出膜中通过同时拉伸来进行。这里,在所述处理的基本相同的阶段,膜在展幅机烘箱中在纵向和横向上拉伸。对于顺序拉伸和同时拉伸两种途径来说,拉伸的程度部分取决于聚酯的性质。但是,所述膜通常拉伸成在各拉伸方向上其取向后的尺寸为原尺寸的2到5倍,更优选2.5到4.5倍。一般来说,拉伸在70℃到150℃,通常70℃到140℃的温度下进行。如果只需在一个方向取向,那么可以采用更大的拉伸比(例如最高达到约8倍)。并不需要在纵向和横向同等拉伸,但是在需要平衡的性质时则优选同等拉伸。In the preferred flat film process, the polyester forming the substrate is extruded through a slot die and rapidly cooled on a cooled casting drum to ensure that the polyester is quenched into an amorphous form. Orientation is then performed by stretching the quenched extrudate in at least one direction at a temperature above the glass transition temperature of the polyester. Subsequent orientation can be performed by a film stretcher to first stretch the flat quenched extrudate in one direction (usually the machine direction, ie the straight direction) and then in the transverse direction. The longitudinal stretching of the extrudate is suitably carried out via a set of rotating rolls or between two pairs of nip rolls, and then the transverse stretching is carried out on a tenter. Alternatively, orientation can be performed in the extruded film by simultaneous stretching. Here, the film is stretched in the machine and transverse directions in a tenter oven at substantially the same stage of the process. For both sequential and simultaneous stretching approaches, the degree of stretching depends in part on the nature of the polyester. However, the film is usually stretched so that its oriented size is 2 to 5 times, more preferably 2.5 to 4.5 times its original size in each direction of stretching. Generally, stretching is performed at a temperature of 70°C to 150°C, usually 70°C to 140°C. Larger draw ratios (eg, up to about 8 times) can be used if orientation is only required in one direction. Equal stretching in the machine and transverse directions is not required, but is preferred when balanced properties are desired.
拉伸膜通过在高于所述聚酯的玻璃化转变温度但低于其熔融温度的温度下,在尺寸限定下热定形诱导聚酯结晶来进行尺寸稳定,正如GB-A-838708中所述。尺寸限定的张力通常在约19-75kg/m膜宽度、优选约45-50kg/m膜宽度的范围,对于约2.6m宽的膜,张力范围为约50-190kg,优选120-130kg。实际热定形温度和时间将根据膜的组成而不同,但应进行选择从而基本上不会降低膜的抗撕裂性。在这些限制中,通常需要约135-250℃的热定形温度,更优选235-240℃的热定形温度。加热时间将取决于所用温度并通常为5到40秒,优选8到30秒。Stretch films are dimensionally stabilized by inducing crystallization of the polyester by heat-setting under dimension constraints at a temperature above the glass transition temperature of said polyester but below its melting temperature, as described in GB-A-838708 . The dimensionally defined tension is generally in the range of about 19-75 kg/m film width, preferably about 45-50 kg/m film width, for a film about 2.6 m wide the tension range is about 50-190 kg, preferably 120-130 kg. The actual heat-setting temperature and time will vary depending on the composition of the film, but should be selected so as not to substantially reduce the tear resistance of the film. Within these constraints, a heat-setting temperature of about 135-250°C is typically required, more preferably a heat-setting temperature of 235-240°C. The heating time will depend on the temperature used and will generally be from 5 to 40 seconds, preferably from 8 to 30 seconds.
然后将完成的膜通过在低张力(即最小可能的尺寸限制)下,在高于聚酯的玻璃化转变温度但低于其熔点的温度下加热而让膜的大部分内在收缩出现(释放)来进一步热稳定,并由此产生具非常低残留收缩率并因此具有高尺寸稳定性的膜。在这种热稳定步骤中膜经受的张力通常低于5kg/m膜宽度,优选低于3.5kg/m,更优选为1-约2.5kg/m,通常为1.5-2kg/m膜宽度。在热稳定步骤中膜的横向尺寸没有增加。热稳定步骤所用的温度可根据最终膜性质所需的组合而不同,温度越高,得到越好即越低的残留收缩性。通常需要135-250℃的温度,优选190-250℃,更优选200-230℃,更优选至少215℃,一般215-230℃。加热时间取决于所用温度,但通常为10到40秒钟,优选20到30秒钟的时间。这种加热稳定处理可通过各种方法来进行,包括平面和垂直结构并“离线”作为单独处理步骤或“在线”作为膜生产过程的继续。在一种实施方案中,热稳定“离线”进行。The completed film is then allowed to occur (release) most of the film's intrinsic shrinkage by heating under low tension (i.e. the smallest possible dimensional constraint) at a temperature above the glass transition temperature of the polyester but below its melting point to further thermally stabilize and thus produce films with very low residual shrinkage and thus high dimensional stability. The tension to which the film is subjected during this thermal stabilization step is generally below 5 kg/m film width, preferably below 3.5 kg/m, more preferably 1 to about 2.5 kg/m, typically 1.5-2 kg/m film width. The transverse dimension of the film did not increase during the thermal stabilization step. The temperature used in the thermal stabilization step can vary depending on the desired combination of final film properties, with higher temperatures giving better ie lower residual shrinkage. Typically a temperature of 135-250°C is required, preferably 190-250°C, more preferably 200-230°C, more preferably at least 215°C, typically 215-230°C. The heating time depends on the temperature used, but is usually a period of 10 to 40 seconds, preferably 20 to 30 seconds. This heat stabilization treatment can be performed by various methods, including planar and vertical configurations and "offline" as a separate processing step or "online" as a continuation of the film production process. In one embodiment, thermal stabilization is performed "off-line".
所述基材可包括一个或多个单独的层。各个层的组成可相同或不同。例如,所述基材可包括一层、两层、三层、四层或五层或更多的层并且典型的多层结构可以是AB、ABA、ABC、ABAB、ABABA或ABCBA型。优选所述基材只包括一层。当所述基材包括多于一层时,基材的制备可方便地通过共挤型来进行,可通过多孔模头的独立模孔同时共挤塑各成膜层,然后结合各仍然熔融的层来进行,或者优选通过单通道共挤塑来进行,其中各聚合物的熔融流首先在通向模头集料管的通道内结合,然后在没有相互混合的直线流动条件下从模孔一起挤出而产生多层聚合物膜,其可如上所述那样取向和热定形。多层基材的形成也可通过常规的层合技术来进行,例如通过将预成的第一层和预成的第二层一起层合来进行,或者通过将第一层浇铸在预成的第二层上来进行。The substrate may comprise one or more individual layers. The compositions of the individual layers may be the same or different. For example, the substrate may comprise one, two, three, four or five or more layers and a typical multilayer structure may be of the AB, ABA, ABC, ABAB, ABABA or ABCBA type. Preferably the substrate comprises only one layer. When the substrate comprises more than one layer, the preparation of the substrate is conveniently carried out by co-extrusion, whereby each film-forming layer is co-extruded simultaneously through separate orifices of a multi-hole die and then combined with each still molten or, preferably, by single-channel coextrusion, in which the melt streams of the individual polymers are first combined in a channel leading to the manifold of the die, and then exit the die orifice together under linear flow conditions without intermingling. Extrusion produces a multilayer polymer film which can be oriented and heat set as described above. Formation of the multilayer substrate can also be carried out by conventional lamination techniques, such as by laminating together a preformed first layer and a preformed second layer, or by casting the first layer on a preformed Go up the second floor.
所述聚合物膜可适当地包含常用于生产聚合物膜的添加剂。因此,可按需要混入试剂诸如交联剂、染料、颜料、成洞剂(voiding agent)、润滑剂、抗氧化剂、自由基清除剂、UV吸收剂、热稳定剂、阻燃剂、防粘连剂、表面活性剂、助滑剂、光亮剂、光泽改良剂、降解助剂、粘度调节剂和分散稳定剂。具体地说,一层可包括可改善生产时的加工性和卷曲性(windability)的特定填料。所述特定填料可以例如是颗粒状无机填料或不相容的树脂填料或两种或多种这种填料的混合物。The polymer film may suitably contain additives commonly used in the production of polymer films. Therefore, agents such as cross-linking agents, dyes, pigments, voiding agents, lubricants, antioxidants, radical scavengers, UV absorbers, heat stabilizers, flame retardants, antiblocking agents can be mixed as required , Surfactants, slip agents, brighteners, gloss improvers, degradation aids, viscosity modifiers and dispersion stabilizers. In particular, one layer may include specific fillers that improve processability and windability during production. The specific filler may for example be a particulate inorganic filler or an incompatible resin filler or a mixture of two or more such fillers.
这里“不相容的树脂”是指在所述膜的挤压和制造中的最高温度下不熔融或者基本上与聚合物不能混合的树脂。不兼容树脂的存在通常导致空隙层,这意味着所述层包括蜂窝状结构,包含至少一定比例的独立封闭的孔隙。适合的不相容树脂包括聚酰胺和烯烃聚合物,特别是分子中含至多6个碳原子的单-α-烯烃的均聚物或共聚物。优选的材料包括低密度或高密度烯烃均聚物(特别是聚乙烯、聚丙烯或聚4-甲基戊烯-1)、烯烃共聚物(特别是乙烯-丙烯共聚物)或两种或多种这些聚合物的混合物。可使用无规、嵌段或接枝共聚物。Here "incompatible resin" means a resin that does not melt or is substantially immiscible with the polymer at the highest temperatures in the extrusion and manufacture of the film. The presence of incompatible resins generally results in a voided layer, which means that the layer comprises a cellular structure containing at least a proportion of independently closed pores. Suitable incompatible resins include polyamides and olefin polymers, especially homopolymers or copolymers of mono-alpha-olefins containing up to 6 carbon atoms in the molecule. Preferred materials include low or high density olefin homopolymers (especially polyethylene, polypropylene or poly-4-methylpentene-1), olefin copolymers (especially ethylene-propylene copolymers) or two or more a mixture of these polymers. Random, block or graft copolymers can be used.
颗粒状无机填料包括常规无机填料,特别是金属或类金属氧化物,诸如氧化铝、二氧化硅(特别是沉淀二氧化硅或含硅藻的二氧化硅和硅胶)和二氧化钛,煅烧瓷土和碱金属盐诸如钙和钡的碳酸盐和硫酸盐。也可使用玻璃颗粒。所述颗粒无机填料可以是空隙或非空隙类型。适合的颗粒无机填料可以是均相填料并基本上由单种填料物质或化合物诸如单独的二氧化钛或硫酸钡组成。或者,至少一部分填料可以为多相,基本填料与另外的改性组分结合。例如,基本填料颗粒可以用表面改性剂诸如颜料、皂、表面活性剂偶合剂或其它改性剂处理以促进或改变填料与基材层聚酯兼容的程度。Particulate inorganic fillers include conventional inorganic fillers, especially metal or metalloid oxides, such as alumina, silica (especially precipitated silica or diatom-containing silica and silica gel) and titanium dioxide, calcined china clay and alkali Metal salts such as calcium and barium carbonates and sulfates. Glass particles can also be used. The particulate inorganic filler can be of the voided or non-voided type. Suitable particulate inorganic fillers may be homogeneous fillers and consist essentially of a single filler substance or compound such as titanium dioxide or barium sulfate alone. Alternatively, at least a portion of the filler may be heterogeneous, with the base filler combined with additional modifying components. For example, the primary filler particles may be treated with surface modifiers such as pigments, soaps, surfactant coupling agents, or other modifiers to facilitate or alter the degree to which the filler is compatible with the substrate layer polyester.
优选的颗粒无机填料包括二氧化钛和二氧化硅。Preferred particulate inorganic fillers include titanium dioxide and silica.
二氧化钛颗粒可以是锐钛矿或金红石晶体型。所述二氧化钛颗粒优选大部分为金红石,更优选至少60%(重量)、特别是至少80%、并特别是约100%(重量)为金红石。所述颗粒可通过标准方法诸如氯化物方法或硫酸盐法制备。所述二氧化钛颗粒可以涂层,优选用无机氧化物诸如铝、硅、锌、镁或其混合物涂层。优选涂层另外包含有机化合物,诸如脂肪酸,优选链烷醇,适合具有8到30个碳原子,优选12到24个碳原子。聚二有机硅氧烷或聚有机氢硅氧烷诸如聚二甲基硅氧烷或聚甲基氢硅氧烷均是合适的有机化合物。所述涂料以水悬浮液的形式适当地施加到二氧化钛颗粒上。无机氧化物从水溶性化合物诸如铝酸钠、硫酸铝、氢氧化铝、硝酸铝、硅酸或硅酸钠沉淀到水悬浮液中。基于二氧化钛的重量,在二氧化钛颗粒上的涂层优选有1-12%的无机氧化物和优选有0.5-3%的有机化合物。The titanium dioxide particles can be in the anatase or rutile crystal form. The titanium dioxide particles are preferably mostly rutile, more preferably at least 60% by weight, especially at least 80%, and especially about 100% by weight rutile. The particles can be prepared by standard methods such as the chloride method or the sulfate method. The titanium dioxide particles may be coated, preferably with inorganic oxides such as aluminum, silicon, zinc, magnesium or mixtures thereof. Preferably the coating additionally comprises organic compounds such as fatty acids, preferably alkanols, suitably having 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms. Polydiorganosiloxanes or polyorganohydrogensiloxanes such as polydimethylsiloxane or polymethylhydrogensiloxane are suitable organic compounds. The coating is suitably applied to the titanium dioxide particles in the form of an aqueous suspension. Inorganic oxides are precipitated into aqueous suspensions from water-soluble compounds such as sodium aluminate, aluminum sulfate, aluminum hydroxide, aluminum nitrate, silicic acid or sodium silicate. The coating on the titanium dioxide particles preferably has 1-12% inorganic oxide and preferably 0.5-3% organic compound, based on the weight of titanium dioxide.
所述无机填料应是细碎的填料,并且其体积分布中值粒径(相当于所有颗粒体积50%的等效球体直径,在体积%对颗粒直径的累积分布曲线上读取,通常称为"D(v,0.5)"值)优选为0.01-7.0μm,更优选0.05-4.5μm,特别是0.15-1.5μm。The inorganic filler should be a finely divided filler with a volume distribution median particle diameter (equivalent spherical diameter equivalent to 50% of the volume of all particles, read on a cumulative distribution curve of volume % versus particle diameter, commonly referred to as " D(v,0.5)"value) is preferably 0.01-7.0 μm, more preferably 0.05-4.5 μm, especially 0.15-1.5 μm.
无机填料颗粒的粒度分布也是一个重要参数,例如过大颗粒的存在可能导致膜展现出难看的“小斑点”,即用裸眼可看见膜中存在一颗颗的填料颗粒。优选不存在实际粒径超过30μm的无机填料颗粒。超过这种尺寸的颗粒可通过本领域人们已知的筛分方法来去除。但是,在除去所有大于所选定尺寸的颗粒方面,筛分并不总是完全成功。所以,实际上,99.9%的无机填料颗粒的尺寸应不超过30μm,优选应不超过20μm,并更优选应不超过10μm。优选至少90%、更优选至少95%体积的无机填料颗粒在平均粒径±3.0μm,特别是±2.5μm的范围内。The particle size distribution of the inorganic filler particles is also an important parameter, for example the presence of oversized particles can cause the film to exhibit unsightly "spots", ie individual filler particles in the film that can be seen with the naked eye. Preferably no inorganic filler particles having a substantial particle size exceeding 30 μm are present. Particles above this size can be removed by sieving methods known in the art. However, sieving is not always completely successful in removing all particles larger than the selected size. So, in practice, 99.9% of the inorganic filler particles should not exceed a size of 30 μm, preferably should not exceed 20 μm, and more preferably should not exceed 10 μm. Preferably at least 90%, more preferably at least 95% by volume of the inorganic filler particles are within the range of mean particle size ± 3.0 μm, especially ± 2.5 μm.
填料颗粒的粒径可通过电子显微镜、考尔特计数器、沉降分析和静态或动态光散射测量。优选基于激光光衍射的技术。所述中值粒径可通过绘制一条代表小于所选粒径的颗粒体积百分比的累积分布曲线并测量第50个百分率来测得。The particle size of filler particles can be measured by electron microscopy, Coulter counter, sedimentation analysis and static or dynamic light scattering. Techniques based on laser light diffraction are preferred. The median particle size can be determined by plotting a cumulative distribution curve representing the volume percent of particles smaller than the selected particle size and measuring the 50th percentile.
膜的组分可以常规方式混合一起。例如,通过与形成所述层聚合物的单体反应剂混合,或所述组分可通过鼓转或干混或通过在挤压机中化合来与聚合物混合,接着冷却并通常粉碎成颗粒或碎片。也可使用母炼胶制备工艺。The components of the film can be mixed together in a conventional manner. For example, by mixing with the monomeric reactants that form the layer polymer, or the components can be mixed with the polymer by tumbling or dry blending or by compounding in an extruder, followed by cooling and usually crushing into granules or fragments. A masterbatch preparation process may also be used.
在一优选的实施方案中,本发明的膜是光学透明的膜,优选按照标准ASTM D1003标准测量,具有<3.5%、优选<2%、更优选<1.5%、再更优选≤1%、特别是小于0.7%的散射可见光(雾度)。在一个实施方案中,雾度在0.6-1%的范围。按照标准ASTM D 1003标准,优选在400-800nm范围的总透光率(TLT)至少为75%,优选至少80%,更优选至少85%。在该实施方案中,填料通常只是少量存在,通常不超过给定层重量的0.5%并优选低于0.2%(重量)。In a preferred embodiment, the film of the present invention is an optically clear film, preferably having <3.5%, preferably <2%, more preferably <1.5%, even more preferably <1%, especially measured according to standard ASTM D1003 It is less than 0.7% of scattered visible light (haze). In one embodiment, the haze is in the range of 0.6-1%. According to standard ASTM D 1003, preferably the total light transmittance (TLT) in the range of 400-800 nm is at least 75%, preferably at least 80%, more preferably at least 85%. In this embodiment, the filler is generally present only in small amounts, usually not more than 0.5% by weight of a given layer and preferably less than 0.2% by weight.
在一实施方案中,所述膜不仅是如上所定义的那样光学透明,而且也展现出良好的加工性能和卷曲性。在该实施方案中,所述膜包含约50-1000ppm体积分布中值粒径为1.0-7.0μm的玻璃颗粒和约200-2000ppm平均基本粒度(就是数均粒径)为0.01-0.09μm的二氧化硅颗粒。所述玻璃颗粒优选为实心玻璃珠,不论选择的观点如何,优选具有基本上圆形的横截面。要求各玻璃颗粒展现出1:1到1:0.5、优选1:1到1:0.8、特别是1:1到1:0.9的长宽比d1:d2(这里d1和d2分别为颗粒的最大和最小尺寸)。所述玻璃颗粒并不受其化学组成的限制,但是优选包括冕玻璃和/或硼硅玻璃。不论选择的观点如何,所述硅石颗粒优选基本上为圆形横截面。典型的基本硅石颗粒需要展现出1:1到1:0.5并优选1:1到1:0.8的长宽比d1:d2。含玻璃和硅石的层的其它实例描述于US-5328755中,该专利公开通过引用并入本文。In one embodiment, the film is not only optically clear as defined above, but also exhibits good processability and curlability. In this embodiment, the film comprises about 50-1000 ppm of glass particles having a volume distribution median particle size of 1.0-7.0 μm and about 200-2000 ppm of glass particles having an average elementary particle size (ie, number average particle size) of 0.01-0.09 μm. silicon particles. The glass particles are preferably solid glass beads, preferably having a substantially circular cross-section, whatever the point of view of choice. Each glass particle is required to exhibit an aspect ratio d 1 :d 2 (here d 1 and d 2 are respectively particle size and size). The glass particles are not limited by their chemical composition, but preferably comprise crown glass and/or borosilicate glass. Regardless of the point of view chosen, the silica particles are preferably substantially circular in cross-section. Typical elementary silica particles need to exhibit an aspect ratio d 1 :d 2 of 1:1 to 1:0.5 and preferably 1:1 to 1:0.8. Other examples of glass and silica containing layers are described in US-5328755, the disclosure of which is incorporated herein by reference.
在另一备选实施方案中,所述膜不透明并且高度填充,优选展现出0.1-2.0、更优选0.2-1.5、更优选0.25-1.25、再更优选0.35-0.75并特别是0.45-0.65的透光密度(TOD)(Sakura Densitometer;PDA65型;透射模式)。所述膜可方便地通过将有效量的不透明剂混入到聚合物共混物中来使其不透明。适合的不透明剂包括如上所述的不相容的树脂填料、颗粒无机填料或两种或多种这种填料的化合物。基于所述层聚合物的重量,在指定层中存在的填料的量优选为1-30%重量,更优选3-20%重量,特别是4-15%重量,尤其是5-10%重量。In another alternative embodiment, the film is opaque and highly filled, preferably exhibiting a permeability of 0.1-2.0, more preferably 0.2-1.5, more preferably 0.25-1.25, still more preferably 0.35-0.75 and especially 0.45-0.65. Optical density (TOD) (Sakura Densitometer; model PDA65; transmission mode). The film may conveniently be rendered opaque by incorporating into the polymer blend an effective amount of an opacifying agent. Suitable opacifiers include incompatible resinous fillers, particulate inorganic fillers or compounds of two or more such fillers as described above. The amount of filler present in a given layer is preferably 1-30% by weight, more preferably 3-20% by weight, especially 4-15% by weight, especially 5-10% by weight, based on the weight of the layer polymer.
不透明膜的表面优选展现出60-120、更优选80-110、特别是90-105、特别是95-100单位的如本文所述测得的白度指数。The surface of the opaque film preferably exhibits a whiteness index, measured as described herein, of 60-120, more preferably 80-110, especially 90-105, especially 95-100 units.
所述PEN膜还可包括一个或多个另外的聚合物层或涂料层。任何涂料均优选“在线”进行。The PEN film may also include one or more additional polymer layers or paint layers. Any coating is preferably done "in-line".
在一实施方案中,在膜的一面,另一涂层可包括“滑润涂层”以改善膜的加工性和卷曲性。一种适合的滑润涂层可以是例如任选还包含诸如在EP-A-0408197中所述的交联剂的丙烯酸和/或甲基丙烯酸聚合物树脂的不连续层,所述专利公开通过引用并入本文。另一可替用润滑涂层可包括如在美国专利5925428号中所公开的硅酸钾涂层,所述专利公开通过引用并入本文。In one embodiment, on one side of the film, another coating may include a "slip coat" to improve the processability and curling of the film. A suitable slip coating may be, for example, a discrete layer of an acrylic and/or methacrylic polymer resin optionally further comprising a crosslinking agent such as described in EP-A-0408197, which is incorporated by reference Incorporated into this article. Another alternative lubricious coating may include a potassium silicate coating as disclosed in US Patent No. 5,925,428, the disclosure of which is incorporated herein by reference.
在一种实施方案中,所述膜涂布有涂底剂层,其改善了膜对随后施加层的粘合性。涂底剂或粘合剂层的性质和特性将取决于随后施加层的性质,但一般可选自丙烯酸酯或甲基丙烯酸酯聚合物树脂。适合的材料包括:In one embodiment, the film is coated with a primer layer which improves the adhesion of the film to subsequently applied layers. The nature and characteristics of the primer or adhesive layer will depend on the nature of the subsequently applied layer, but may generally be selected from acrylate or methacrylate polymer resins. Suitable materials include:
(i)(a)35-40%(摩尔)丙烯酸烷基酯、(b)35-40%甲基丙烯酸烷基酯、(c)10-15%(摩尔)含游离羧基的共聚单体如衣康酸和(d)15-20%(摩尔)芳族磺酸和/或其盐诸如对苯乙烯磺酸的共聚物,其一个例子是如在EP-A-0429179中公开的包含37.5/37.5/10/15%(摩尔)比例的丙烯酸乙酯/甲基丙烯酸甲酯/衣康酸/对苯乙烯磺酸和/或其盐的共聚物,所述专利公开通过引用并入本文;和(i) (a) 35-40% (mol) alkyl acrylate, (b) 35-40% alkyl methacrylate, (c) 10-15% (mol) comonomers containing free carboxyl groups such as Copolymers of itaconic acid and (d) 15-20 mole % aromatic sulfonic acids and/or salts thereof such as p-styrenesulfonic acid, an example of which is disclosed in EP-A-0429179 comprising 37.5/ A copolymer of ethyl acrylate/methyl methacrylate/itaconic acid/p-styrene sulfonic acid and/or salts thereof in a ratio of 37.5/10/15% by mole, the publication of which is incorporated herein by reference; and
(ii)一种丙烯酸和/或甲基丙烯酸聚合物树脂,其一个例子是如在EP-A-0408197中公开的包含约35-60%(摩尔)丙烯酸乙酯、约30-55%(摩尔)甲基丙烯酸甲酯和约2-20%(摩尔)甲基丙烯酰胺的聚合物,所述专利公开通过引用并入本文。(ii) an acrylic and/or methacrylic polymer resin, an example of which is disclosed in EP-A-0408197 comprising about 35-60 mole % ethyl acrylate, about 30-55 mole % ) methyl methacrylate and about 2-20 mole percent methacrylamide, the disclosure of which is incorporated herein by reference.
所述涂底剂层或粘合剂层也可包含交联剂,其起到交联所述组合物而改善对基材的粘合性并也应能在组合物内进行内交联。适合的交联剂包括蜜胺与甲醛的任选烷氧基化的缩合产物。涂底剂层或粘合剂层也可包含交联催化剂诸如硫酸铵来促进交联剂的交联。其它适合的交联剂和催化剂公开于EP-A-0429179,该专利公开通过引用并入本文。The primer layer or adhesive layer may also contain a crosslinking agent which acts to crosslink the composition to improve adhesion to the substrate and should also be capable of internal crosslinking within the composition. Suitable crosslinkers include the optionally alkoxylated condensation products of melamine and formaldehyde. The primer layer or adhesive layer may also contain a crosslinking catalyst such as ammonium sulfate to facilitate crosslinking of the crosslinking agent. Other suitable crosslinkers and catalysts are disclosed in EP-A-0429179, the disclosure of which is incorporated herein by reference.
使用时,所述膜也可如上所述涂布阻隔层。这种涂层为本领域人们所熟悉并通常在高温下以喷镀法施加。适用于形成阻隔层的材料公开于例如美国专利6,198,217中。一有机阻隔层可由例如可光固化单体或低聚物或热塑性树脂形成。可光固化单体或低聚物应具有低的挥发性和高的熔点。这种单体的例子包括丙烯酸三羟甲酯类,诸如三羟甲基丙烷三丙烯酸酯、双(三羟甲基丙烷)四丙烯酸酯等;长链丙烯酸酯诸如1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯等;和环己基丙烯酸酯类诸如二环戊烯氧乙基丙烯酸酯、二环戊烯氧基丙烯酸酯、甲基丙烯酸环己酯等。这种低聚物的例子包括丙烯酸酯低聚物、环氧丙烯酸酯低聚物、尿烷丙烯酸酯低聚物、醚丙烯酸酯低聚物等。可使用光引发剂诸如苯偶姻醚、二苯酮、乙酰苯、缩酮等来固化树脂。适合的热塑性树脂的例子包括聚乙烯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二酯等。这些有机材料可通过任何本领域人们熟悉的常规技术诸如通过真空沉积来施加。When used, the film may also be barrier coated as described above. Such coatings are well known in the art and are usually applied by spraying at elevated temperatures. Materials suitable for use in forming barrier layers are disclosed, for example, in US Patent 6,198,217. An organic barrier layer can be formed from, for example, photocurable monomers or oligomers or thermoplastic resins. The photocurable monomer or oligomer should have low volatility and high melting point. Examples of such monomers include trimethylol acrylates such as trimethylolpropane triacrylate, bis(trimethylolpropane) tetraacrylate, etc.; long chain acrylates such as 1,6-hexanediol diacrylate; Acrylates, 1,6-hexanediol dimethacrylate, etc.; and cyclohexyl acrylates such as dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyacrylate, cyclohexyl methacrylate, etc. . Examples of such oligomers include acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, ether acrylate oligomers, and the like. The resin can be cured using photoinitiators such as benzoin ethers, benzophenones, acetophenones, ketals, and the like. Examples of suitable thermoplastic resins include polyethylene, polymethylmethacrylate, polyethylene terephthalate, and the like. These organic materials may be applied by any conventional technique familiar to those skilled in the art, such as by vacuum deposition.
无机阻隔层应由展现出低湿气透过性和对湿气稳定的材料制成。例子包括氧化物诸如SiO2、SiO、GeO、Al2O3等,氮化物诸如TiN、Si3N4等,和金属诸如Al、Ag、Au、Pt、Ni等。无机材料可在标准条件下使用汽相技术诸如真空沉积、喷镀等来施加。The inorganic barrier layer should be made of a material that exhibits low moisture vapor transmission and is stable against moisture. Examples include oxides such as SiO2 , SiO, GeO, Al2O3 , etc., nitrides such as TiN, Si3N4 , etc. , and metals such as Al, Ag, Au, Pt, Ni, etc. Inorganic materials can be applied using vapor phase techniques such as vacuum deposition, sputtering, etc. under standard conditions.
阻隔层可本身包括一个或多个分散层,并可包括一个或多个有机层和一个或多个无机层。The barrier layer may itself comprise one or more dispersed layers, and may comprise one or more organic layers and one or more inorganic layers.
在一优选的实施方案中,阻隔层是将光电子器件中基材的水蒸气透过率降低到低于10-6g/m2/天和将氧气透过率降低到低于10-5/mL/m2/天的层。在另一可替用实施方案中,阻隔层是将电子器件中基材的水蒸气透过率降低到低于10-2g/m2/天(优选低于10-6g/m2/天)和将氧气透过率降低到低于10-3/mL/m2/天(优选低于10-5/mL/m2/天)的膜。In a preferred embodiment, the barrier layer is one that reduces the water vapor transmission rate of the substrate in the optoelectronic device to below 10 -6 g/m 2 /day and the oxygen transmission rate to below 10 -5 / Layer in mL/m 2 /day. In another alternative embodiment, the barrier layer is one that reduces the water vapor transmission rate of the substrate in the electronic device to below 10 −2 g/m 2 /day (preferably below 10 −6 g/m 2 /day). days) and membranes that reduce the oxygen transmission rate to less than 10 -3 /mL/m 2 /day (preferably less than 10 -5 /mL/m 2 /day).
一旦沉积了阻隔层,随后的层(包括电极和导电共轭聚合物)可按照本领域人们熟悉的常规生产技术施加。所述电极可以是任何本领域人们熟悉的电极,例如选自本文所述的那些电极。在一种实施方案中,所述电极是导电金属氧化物,优选氧化铟锡。Once the barrier layer is deposited, subsequent layers, including electrodes and conductive conjugated polymers, can be applied according to conventional production techniques familiar to those skilled in the art. The electrodes may be any electrodes known in the art, for example selected from those described herein. In one embodiment, the electrode is a conductive metal oxide, preferably indium tin oxide.
本文通常所指的电子器件和光电子器件包括一个(或多个)导电共轭聚合物层、两个或多个电极和一个或多个基材层。Electronic and optoelectronic devices, as generally referred to herein, include one (or more) conductive conjugated polymer layers, two or more electrodes, and one or more substrate layers.
在本发明的一个实施方案中,术语场致发光显示器件,特别是有机发光显示器(OLED)器件是指包括置于两个各自包含电极的层之间的发光导电共轭聚合物材料层的显示器器件,其中得到的复合结构置于两个基材(或载体或覆盖体)层之间。In one embodiment of the invention, the term electroluminescent display device, in particular an organic light emitting display (OLED) device, refers to a display comprising a layer of light emitting conductive conjugated polymer material placed between two layers each comprising an electrode Devices in which the resulting composite structure is placed between two substrate (or carrier or cover) layers.
在本发明的一个实施方案中,术语光电池(光电伏打电池)是指包括置于两个各自包含电极的层之间的导电共轭聚合物材料层的器件,其中得到的复合结构置于两个基材(或载体或覆盖体)层之间。In one embodiment of the present invention, the term photovoltaic cell (photovoltaic cell) refers to a device comprising a layer of conductive conjugated polymer material interposed between two layers each containing an electrode, wherein the resulting composite structure is interposed between the two layers. between the substrate (or carrier or cover) layers.
在本发明的一个实施方案中,术语晶体管是指一种包括至少一个导电共轭聚合物层、一个门电极、一个源电极和一个漏极以及一个或多个基材层的器件。In one embodiment of the invention, the term transistor refers to a device comprising at least one conductive conjugated polymer layer, a gate electrode, a source electrode and a drain electrode, and one or more substrate layers.
按照本发明的另一方面,提供了一种包括基材层和在其表面上的阻隔层的复合膜,其中所述基材是包含聚萘二甲酸乙二醇酯的热稳定、热定形、取向膜,其在230℃、30分钟具有低于1%的收缩率,并优选其中所述膜在从8℃加热到200℃并然后冷却到8℃前后,在25℃测得的剩余尺寸变化△Lr低于原尺寸的0.75%;并优选在-40℃到+100℃的温度范围内具有低于40×10-6/℃的线性热膨胀系数(CLTE)。在一种实施方案中,所述基材通过包括下面步骤的方法获得:According to another aspect of the present invention, there is provided a composite film comprising a substrate layer and a barrier layer on a surface thereof, wherein the substrate is a heat-stable, heat-set, Oriented film having a shrinkage of less than 1% at 230°C for 30 minutes, and preferably wherein the film has a residual dimensional change measured at 25°C before and after heating from 8°C to 200°C and then cooling to 8°C ΔL r is lower than 0.75% of original size; and preferably has a coefficient of linear thermal expansion (CLTE) lower than 40×10 −6 /°C in the temperature range from -40°C to +100°C. In one embodiment, said substrate is obtained by a method comprising the steps of:
(i)形成包含聚萘二甲酸乙二醇酯的层;(i) forming a layer comprising polyethylene naphthalate;
(ii)在至少一个方向拉伸所述层;(ii) stretching the layer in at least one direction;
(iii)在尺寸限定下以约19-75kg/m膜宽的张力在高于聚酯的玻璃化转变温度但低于其熔点温度的温度下热定形;和(iii) heat-set at a temperature above the glass transition temperature of the polyester but below its melting point temperature at a tension of about 19-75 kg/m film width under dimensional constraints; and
(iv)在低于5kg/m膜宽度的张力和在高于聚酯的玻璃化转变温度但低于其熔点温度的温度下热稳定。(iv) Thermally stable at a tension lower than 5 kg/m film width and at a temperature higher than the glass transition temperature of the polyester but lower than its melting point temperature.
按照本发明的另一方面,提供了一种复合膜,其包括如本文所述的基材层和如本文所述的在其表面上的阻隔层,并还包括在阻隔层表面的至少一部分上的电极层,和任选还包括一共轭导电聚合物层。According to another aspect of the present invention there is provided a composite film comprising a substrate layer as described herein and a barrier layer as described herein on its surface, and further comprising on at least a part of the surface of the barrier layer The electrode layer, and optionally also includes a conjugated conductive polymer layer.
按照本发明的另一方面,提供了一种制备含共轭导电聚合物和基材的如本文所述的电子器件或光电子器件的方法,所述方法包括下面步骤:According to another aspect of the present invention there is provided a method of preparing an electronic or optoelectronic device as described herein comprising a conjugated conductive polymer and a substrate, said method comprising the steps of:
(i)形成包含聚萘二甲酸乙二醇酯的层;(i) forming a layer comprising polyethylene naphthalate;
(ii)在至少一个方向拉伸所述层;(ii) stretching the layer in at least one direction;
(iii)在尺寸限定下以约19-75kg/m膜宽并优选约45-50kg/m膜宽的张力在高于聚酯的玻璃化转变温度但低于其熔点温度的温度下热定形;和(iii) heat-setting at a temperature above the glass transition temperature of the polyester but below its melting point temperature under dimensional constraints at a tension of about 19-75 kg/m film width and preferably about 45-50 kg/m film width; and
(iv)在低于5kg/m膜宽、更优选低于3.5kg/m膜宽、更优选1.0-2.5kg/m膜宽并通常为1.5-2.0kg/m膜宽的张力和在高于聚酯的玻璃化转变温度但低于其熔点温度的温度下热稳定;和(iv) Tension at less than 5 kg/m film width, more preferably less than 3.5 kg/m film width, more preferably 1.0-2.5 kg/m film width and usually 1.5-2.0 kg/m film width and at a tension above thermally stable at temperatures below the glass transition temperature of the polyester but below its melting point temperature; and
(v)提供器件中作为基材的热稳定、热定形、取向膜。(v) Provide thermally stable, heat set, oriented films as substrates in devices.
在电子器件或光电子器件的生产中的步骤还可包括用阻隔层涂布热稳定、热定形的取向膜基材;通过在阻隔层的至少一部分上施加导电材料提供电极;和提供导电共轭聚合物层。The steps in the production of electronic or optoelectronic devices may also include coating a thermally stable, heat-set alignment film substrate with a barrier layer; providing electrodes by applying a conductive material on at least a portion of the barrier layer; and providing conductive conjugated polymeric object layer.
可使用下面试验方法测定聚合物膜的某些性质:Certain properties of polymer films can be determined using the following test methods:
(i)膜透明性可按照ASTM D-1003-61,通过使用Gardner XL211浊度计测定通过整个膜厚度的总透光率(TLT)和雾度(散射透过可见光的百分比)来评价。(i) Film transparency can be evaluated in accordance with ASTM D-1003-61 by measuring total light transmittance (TLT) and haze (percentage of scattered transmitted visible light) through the entire film thickness using a Gardner XL211 turbidimeter.
(ii)膜的透射光密度(TOD)使用Macbeth Densitometer TR 927(Dent & Woods Ltd,Basingstoke,UK)在透射模式下测定。(ii) The transmitted optical density (TOD) of the films was determined in transmission mode using a Macbeth Densitometer TR 927 (Dent & Woods Ltd, Basingstoke, UK).
(iii)尺寸稳定性可就或者(a)线性热膨胀系数(CLTE)或者(b)温度循环法(在将膜加热到指定温度并随后冷却后测量其中沿指定轴的长度变化余量)来评价。(iii) Dimensional stability can be evaluated in terms of either (a) coefficient of linear thermal expansion (CLTE) or (b) temperature cycling (measurement of the margin of change in length along a specified axis in the film after heating it to a specified temperature and then cooling it) .
两种测量方法均使用按照用于温度、位移、力、本征变形、基线和炉温定位的已知方法校准和检查的Thermomechanical AnalyserPE-TMA-7(Perkin Elmer)进行。所述膜使用伸长分析夹(extensionanalysis clamps)测定。伸长夹所需的基线使用非常低膨胀系数的样品(石英)获得,CLTE精密度和准确度(取决于扫描后基线去减)使用已知CLTE值的标准物质如纯的铝箔来评价。选自原有膜样内已知定位轴的样品使用约12mm的夹隔距安装在系统中,并置于在5mm宽度上施加75mN的力下。施加力按照膜厚度调节,即确保一致的张力,并且膜沿分析轴并不弯曲。样品长度标准化成在23℃温度下测定的长度。Both measurements were performed using a Thermomechanical Analyzer PE-TMA-7 (Perkin Elmer) calibrated and checked according to known methods for temperature, displacement, force, intrinsic deformation, baseline and furnace temperature positioning. The films were assayed using extension analysis clamps. The required baseline for the elongation clamp is obtained using a very low coefficient of expansion sample (quartz), and CLTE precision and accuracy (depending on post-scan baseline subtraction) are evaluated using a standard material of known CLTE value such as pure aluminum foil. A sample selected from a known orientation axis within the original film sample was mounted in the system using a clamp gap of approximately 12 mm and placed under a force of 75 mN applied across a width of 5 mm. The applied force is adjusted according to the membrane thickness, i.e. ensuring consistent tension and no bending of the membrane along the analytical axis. The sample length was normalized to the length measured at a temperature of 23°C.
在CLTE测试方法(a)中,样品被冷却到8℃、稳定后以5℃/min从8℃加热到240℃。CLTE值(α)从下式得到:In CLTE test method (a), the sample is cooled to 8°C, stabilized and then heated from 8°C to 240°C at 5°C/min. The CLTE value (α) is obtained from:
α=△L/(L×(T2-T1))α=ΔL/(L×(T 2 -T 1 ))
式中△L为测定的在温度变化(T2-T1)范围内样品长度的变化,L为23℃下的原样品长度。直到Tg温度(120℃),CLTE值都被认为是可靠的。In the formula, ΔL is the change of sample length measured within the range of temperature change (T 2 -T 1 ), and L is the original sample length at 23°C. The CLTE values are considered reliable up to the Tg temperature (120°C).
所述数据可作为标准化到23℃的样品长度随温度变化(%)的函数画图。The data can be plotted as a function of the change in sample length (%) normalized to 23°C as a function of temperature.
在温度循环测试方法(b)中,使用类似于方法(a)的步骤,其中温度在8℃和几个升高的温度之间循环。这样,膜样品从8℃加热到140℃、160℃、180℃或200℃,然后冷却到8℃。在这种处理前后测定在25℃沿横向和纵向的长度,长度变化△Lr计算成原长度的百分比。结果如表2所示。In temperature cycling test method (b), a procedure similar to method (a) was used, where the temperature was cycled between 8°C and several elevated temperatures. In this way, film samples were heated from 8°C to 140°C, 160°C, 180°C, or 200°C, and then cooled to 8°C. The lengths along the transverse and longitudinal directions at 25°C were measured before and after this treatment, and the length change ΔL r was calculated as a percentage of the original length. The results are shown in Table 2.
(iv)特性粘度(IV)使用下面步骤通过熔体粘度测定法测定。在已知温度和压力下通过校准模头的预干燥挤出物的流动速率通过与计算机相连的转换器测量。计算机程序从实验测得的回归方程计算熔体粘度值(log10粘度)和等效IV。通过计算机绘制IV对时间(分钟)的图并计算降解速率。将图外推到0时间得到起始IV和等效熔体粘度。模孔直径为0.020英寸,对于最高0.80的IV,熔体温度为284℃,对于>0.80的IV,熔体温度为295℃。(iv) Intrinsic viscosity (IV) was determined by melt viscometry using the following procedure. The flow rate of the pre-dried extrudate through the calibrated die at known temperature and pressure was measured by a transducer linked to a computer. The computer program calculates melt viscosity values (log 10 viscosity) and equivalent IV from the experimentally measured regression equation. The IV is plotted against time (minutes) by computer and the degradation rate is calculated. Extrapolating the graph to time 0 gives the starting IV and equivalent melt viscosity. The die hole diameter was 0.020 inches and the melt temperature was 284°C for IV up to 0.80 and 295°C for IV >0.80.
(v)在指定温度的收缩率通过将样品置于加热炉中一段预定时间来测量。计算以加热前后在指定方向膜的尺寸变化率%计的收缩率%。(v) Shrinkage at a specified temperature is measured by placing the sample in a heating furnace for a predetermined period of time. Shrinkage % was calculated as % dimensional change of the film in the specified direction before and after heating.
(vi)表面粗糙度使用本领域人们熟悉的常规的非接触、白光、相转变干涉量度分析技术测量。所用的仪器为Wyko NT3300表面轮廓测定仪。可使用该技术获得的有用特征数据包括:(vi) Surface roughness is measured using conventional non-contact, white light, phase transition interferometry analytical techniques familiar to those skilled in the art. The instrument used is a Wyko NT3300 surface profilometer. Useful characterization data that can be obtained using this technique include:
平均粗糙度(Ra):由测量表面积计算得到的数学平均峰高Average Roughness (Ra): The mathematical average peak height calculated from the measured surface area
均方根粗糙度(Rq):由测量表面积计算得到的平均峰高均方根Root mean square roughness (Rq): average peak height root mean square calculated from the measured surface area
最大剖面峰高(Rp):在测量表面积中最高峰的峰高Maximum Profile Peak Height (Rp): The peak height of the highest peak in the measured surface area
平均最大剖面峰高(Rpm):在测量表面积中十个最高峰的平均值。Average Maximum Profile Peak Height (Rpm): The average of the ten highest peaks in the measured surface area.
粗糙度参数和峰高按照常规技术相对于平均水平的样品表面积或“平均线”来测量。(聚合物膜表面可能并不完全平,经常沿其表面有轻微的起伏。所述平均线是从起伏和表面高度偏离的中部通过的一条直线,其平分纵断面而使平均线上下方具有相同面积。)Roughness parameters and peak heights are measured relative to the average level of sample surface area or "mean line" according to conventional techniques. (Polymer film surfaces may not be perfectly flat, and often have slight undulations along their surface. The mean line is a straight line passing through the middle of the undulations and surface height deviations, which bisects the profile so that the mean line has the same area.)
表面轮廓分析通过扫描在表面轮廓分析机的“视场”(其是单次测量中扫描的面积)内膜表面的离散区域来进行。膜样品可使用离散视场或通过扫描连续视场形成陈列来分析。此中进行的分析使用高清晰度的Wyko NT3300表面轮廓分析仪,其中每个视场包括736×480像素。Surface profiling is performed by scanning discrete regions of the intima surface over the "field of view" of the surface profiling machine (which is the area scanned in a single measurement). Film samples can be analyzed using a discrete field of view or by scanning a continuous field of view to form an array. The analysis performed here used a high-resolution Wyko NT3300 surface profiler, where each field of view comprised 736 x 480 pixels.
对于Ra和Rq的测量来说,使用具有50倍放大率的物镜来提高分辨率。得到的视场具有90μm×120μm的尺寸,并具0.163μm的像素尺寸。For Ra and Rq measurements, an objective lens with 50X magnification was used to increase the resolution. The resulting field of view has dimensions of 90 μm x 120 μm, with a pixel size of 0.163 μm.
对于Rp和Rpm的测量来说,使用具有10倍放大率连同“0.5倍视场倍增器”给出5倍的总放大率来方便地提高分辨率。得到的视场具有0.9mm×1.2mm的尺寸,伴随着1.63μm的像素尺寸。For the measurement of Rp and Rpm it is convenient to use a 10x magnification together with a "0.5x field multiplier" giving a total magnification of 5x to increase the resolution. The resulting field of view has dimensions of 0.9 mm x 1.2 mm, with a pixel size of 1.63 μm.
对每个测量来说,五个连续扫描结果一起得到一个平均值。所述测量使用10%的调制阈值(信噪比),即低于阈值的数据被弃去。For each measurement, five consecutive scans are combined to obtain an average value. The measurements use a modulation threshold (signal-to-noise ratio) of 10%, ie data below the threshold are discarded.
优选本发明的膜具有低于0.8、优选低于0.7、优选低于0.65并最优选低于0.6nm的如本文所述测量的Ra值。优选本发明的膜具有1.0nm或以下、优选0.9nm或以下、以下0.85nm或以下、最优选0.75nm或以下如本文中所述测量的Rq值。Preferably films of the invention have a Ra value measured as described herein below 0.8, preferably below 0.7, preferably below 0.65 and most preferably below 0.6 nm. Preferably the films of the invention have an Rq value of 1.0 nm or less, preferably 0.9 nm or less, 0.85 nm or less, most preferably 0.75 nm or less, measured as described herein.
(vii)氧气透过率可使用ASTM D3985测量。(vii) Oxygen transmission rate can be measured using ASTM D3985.
(viii)水蒸气透过率可使用ASTM F1249测量。(viii) Water vapor transmission rate can be measured using ASTM F1249.
(ix)膜外表面的白度指数使用Colorgard System 2000,Model/45(Pacific Scientific)按照ASTM D313来测量。(ix) The whiteness index of the outer surface of the film is measured according to ASTM D313 using Colorgard System 2000, Model/45 (Pacific Scientific).
具体实施方式 Detailed ways
本发明将通过下面实施例来进一步说明。应理解所述实施例只是用于说明而并不对上述的本发明构成限定。在没有背离本发明的情况下可做细节上的修改。The invention will be further illustrated by the following examples. It should be understood that the examples are for illustration only and do not limit the invention described above. Changes in detail may be made without departing from the invention.
实施例Example
实施例1Example 1
在标准酯交换反应中,使萘二甲酸二甲酯在400ppm乙酸锰四水合物催化剂的存在下与乙二醇反应,形成萘二甲酸二(2-羟乙基)酯及其低聚物。在酯交换反应末期,加入0.025%磷酸稳定剂,接着加入0.04%三氧化锑缩聚催化剂。进行标准分批缩聚反应直到聚萘二甲酸乙二醇酯的特性粘度(IV)为约0.50-0.675(真实PEN IV;PET等效IV0.75-1.00)。In a standard transesterification reaction, dimethyl naphthalate is reacted with ethylene glycol in the presence of 400 ppm manganese acetate tetrahydrate catalyst to form bis(2-hydroxyethyl) naphthalate and its oligomers. At the end of the transesterification reaction, 0.025% phosphoric acid stabilizer was added, followed by 0.04% antimony trioxide polycondensation catalyst. Standard batch polycondensation reactions were carried out until the polyethylene naphthalate had an intrinsic viscosity (IV) of about 0.50-0.675 (true PEN IV; PET equivalent IV 0.75-1.00).
包含PEN的聚合物组合物被挤出并浇铸在热的旋转抛光鼓上。然后将膜送到前行拉制单元并在那里经一系列温控辊在挤出方向拉伸到其原尺寸的约3.34倍。拉制温度为约133℃。然后将膜通过138℃下的展幅机烘箱中并且在那里将膜在横向上拉伸到其原尺寸的约4.0倍。然后将该双轴拉伸膜在冷却和卷到卷轴前通过常规方法在最高可达约238℃的温度下热定形。膜总厚度为125μm。A polymer composition comprising PEN was extruded and cast on a hot rotating polishing drum. The film was then sent to a preceding draw unit where it was stretched to about 3.34 times its original dimension in the extrusion direction over a series of temperature controlled rolls. The drawing temperature was about 133°C. The film was then passed through a tenter oven at 138°C where the film was stretched in the cross direction to about 4.0 times its original size. The biaxially stretched film is then heat set by conventional methods at temperatures up to about 238°C before being cooled and rolled onto rolls. The total film thickness was 125 μm.
然后将热定形的双轴拉伸膜展开并顺序通过一系列四个浮选炉并通过施加与控制所述膜的输送相匹配的最小线张力让其松弛。然后将热稳定的膜卷起来。四个炉的每一个均在横向具有三个控温区(左、中和右):The heat-set biaxially stretched film was then unrolled and sequentially passed through a series of four flotation ovens and allowed to relax by applying a minimum line tension matched to the controlled transport of the film. The thermally stable film is then rolled up. Each of the four furnaces has three temperature-controlled zones in the transverse direction (left, center and right):
在热稳定步骤中膜的线速度为15m/min。用于膜(1360mm原辊宽度)的张力为24-25N。The line speed of the film during the thermal stabilization step was 15 m/min. The tension used for the film (1360mm raw roll width) was 24-25N.
实施例2Example 2
在热稳定步骤中使用下面温度重复实施例1的步骤:The procedure of Example 1 was repeated in the heat stabilization step using the following temperatures:
实施例3Example 3
在标准酯交换反应中,使萘二甲酸二甲酯在400ppm乙酸锰催化剂的存在下与乙二醇反应(二醇:酯摩尔比率为2.1:1),形成萘二甲酸二(2-羟乙基)酯及其低聚物。在酯交换反应末期,加入0.025%磷酸稳定剂,接着加入0.020%二氧化锗缩聚催化剂(133ppm Ge金属)。进行标准分批缩聚反应直到聚萘二甲酸乙二醇酯的特性粘度(IV)为约0.50-0.675(真实PEN IV;PET等效IV 0.75-1.00)。按照实施例1中所述的通用步骤将得到的聚酯用于制备膜。In a standard transesterification reaction, dimethyl naphthalate is reacted with ethylene glycol in the presence of 400 ppm manganese acetate catalyst (diol:ester molar ratio 2.1:1) to form di(2-hydroxyethyl naphthalate) base) esters and their oligomers. At the end of the transesterification reaction, 0.025% phosphoric acid stabilizer was added, followed by 0.020% germanium dioxide polycondensation catalyst (133ppm Ge metal). Standard batch polycondensation reactions were carried out until the polyethylene naphthalate had an intrinsic viscosity (IV) of about 0.50-0.675 (true PEN IV; PET equivalent IV 0.75-1.00). The resulting polyester was used to prepare films following the general procedure described in Example 1.
实施例4Example 4
在标准酯交换反应中,使萘二甲酸二甲酯在210ppm乙酸锰四水合物催化剂的存在下与乙二醇反应,形成萘二甲酸二(2-羟乙基)酯及其低聚物。在酯交换反应末期,加入0.025wt%磷酸稳定剂,接着加入0.036wt%三氧化锑缩聚催化剂。进行标准分批缩聚反应直到聚萘二甲酸乙二醇酯的特性粘度(IV)为约0.50-0.675(真实PEN IV;PET等效IV0.75-1.0)。按照实施例1中所述的步骤将聚酯用于制备膜,不同之处在于前行拉伸在3.1的拉伸比和150-155℃的温度下进行;横向拉伸在3.5的拉伸比和145℃的温度下进行并且热定形温度为234℃。最终膜厚度为125μm并且雾度为0.6%。In a standard transesterification reaction, dimethyl naphthalate is reacted with ethylene glycol in the presence of 210 ppm manganese acetate tetrahydrate catalyst to form bis(2-hydroxyethyl) naphthalate and its oligomers. At the end of the transesterification reaction, 0.025wt% phosphoric acid stabilizer was added, followed by 0.036wt% antimony trioxide polycondensation catalyst. Standard batch polycondensation was performed until the polyethylene naphthalate had an intrinsic viscosity (IV) of about 0.50-0.675 (true PEN IV; PET equivalent IV 0.75-1.0). The polyester was used to prepare the film according to the procedure described in Example 1, except that the forward stretching was carried out at a draw ratio of 3.1 and a temperature of 150-155°C; the transverse stretch was carried out at a draw ratio of 3.5 and a temperature of 145°C and a heat setting temperature of 234°C. The final film thickness was 125 μm and the haze was 0.6%.
使用本文中所述的试验分析实施例1和2的膜的收缩率,结果列于表1。将在没有热稳定步骤下以与实施例1相同的方式制备的PEN膜用作对照(对照1)。The films of Examples 1 and 2 were analyzed for shrinkage using the test described herein and the results are listed in Table 1. A PEN film prepared in the same manner as in Example 1 without the heat stabilization step was used as a control (Control 1).
表1:膜收缩率Table 1: Film Shrinkage
表1的结果表明即使在较高温度下,所述热稳定处理的热定形膜也具有良好的尺寸稳定性。结果还表明较高温度的热稳定处理得到改善的收缩率性质(实施例2)。The results in Table 1 show that the heat-stabilized heat-set films have good dimensional stability even at higher temperatures. The results also show that higher temperature heat stabilization treatments lead to improved shrinkage properties (Example 2).
使用上述的尺寸稳定性试验方法(iii)(b)分析实施例3和4的膜。将按实施例4制备但没有热稳定化处理的PEN膜用作对照(对照2)。在膜的横向(TD)和纵向(MD)进行测量。负值代表膜收缩。结果列于表2。The films of Examples 3 and 4 were analyzed using Dimensional Stability Test Method (iii)(b) above. A PEN film prepared as in Example 4 but without heat stabilization was used as a control (Control 2). Measurements are made in the transverse direction (TD) and machine direction (MD) of the film. Negative values represent membrane shrinkage. The results are listed in Table 2.
表2.样品长度的剩余变化△Lr Table 2. Remaining change in sample length ΔL r
表2中的数据表明热稳定的PEN膜暴露于高温时只展现出非常小的永久尺寸变化。因此就作为温度函数的尺寸稳定性来说这种膜拥有有利和可预测的性质并将适合在电子显示器中作为基材。相反,没有热稳定处理的PEN膜展现出收缩和膨胀作用,导致膜较大的永久变形,特别是最初的加热阶段后。The data in Table 2 indicate that thermally stable PEN films exhibit only very little permanent dimensional change when exposed to high temperatures. Such films thus possess favorable and predictable properties in terms of dimensional stability as a function of temperature and will be suitable as substrates in electronic displays. In contrast, the PEN film without heat stabilization treatment exhibited shrinkage and expansion effects, resulting in a larger permanent deformation of the film, especially after the initial heating stage.
膜的表面粗糙度也采用本文所述的方法测量,其结果列于表3。The surface roughness of the film was also measured using the method described herein, and the results are listed in Table 3.
表3.表面粗糙度Table 3. Surface Roughness
表3的结果表明用Ge-催化的聚酯获得了优异的光滑度。The results in Table 3 show that excellent smoothness was obtained with the Ge-catalyzed polyester.
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Also Published As
Publication number | Publication date |
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CN102785419B (en) | 2015-01-14 |
CN1553856A (en) | 2004-12-08 |
DE60223298T2 (en) | 2008-08-14 |
JP2010114096A (en) | 2010-05-20 |
EP1425170A1 (en) | 2004-06-09 |
US7101627B2 (en) | 2006-09-05 |
WO2003022575A1 (en) | 2003-03-20 |
HK1065513A1 (en) | 2005-02-25 |
EP1640154A1 (en) | 2006-03-29 |
JP4623961B2 (en) | 2011-02-02 |
DE60208913T2 (en) | 2006-09-14 |
TW583233B (en) | 2004-04-11 |
JP5238733B2 (en) | 2013-07-17 |
JP2005521193A (en) | 2005-07-14 |
CN102785420A (en) | 2012-11-21 |
KR100857960B1 (en) | 2008-09-09 |
KR100915479B1 (en) | 2009-09-03 |
CN100421926C (en) | 2008-10-01 |
EP1640154B1 (en) | 2007-10-31 |
CN102785419A (en) | 2012-11-21 |
DE60208913D1 (en) | 2006-04-13 |
DE60223298D1 (en) | 2007-12-13 |
EP1425170B1 (en) | 2006-01-25 |
KR20040033039A (en) | 2004-04-17 |
KR20070072631A (en) | 2007-07-04 |
US20040247916A1 (en) | 2004-12-09 |
US20060275591A1 (en) | 2006-12-07 |
US7300703B2 (en) | 2007-11-27 |
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